EP3796434A1 - Binder aqueous solution for lithium-ion battery, slurry for lithium-ion battery negative electrode, negative electrode for lithium-ion battery, and lithium-ion battery - Google Patents
Binder aqueous solution for lithium-ion battery, slurry for lithium-ion battery negative electrode, negative electrode for lithium-ion battery, and lithium-ion battery Download PDFInfo
- Publication number
- EP3796434A1 EP3796434A1 EP20196109.1A EP20196109A EP3796434A1 EP 3796434 A1 EP3796434 A1 EP 3796434A1 EP 20196109 A EP20196109 A EP 20196109A EP 3796434 A1 EP3796434 A1 EP 3796434A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- mass
- lithium
- mol
- meth
- ion battery
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 84
- 239000002002 slurry Substances 0.000 title claims abstract description 61
- 239000007864 aqueous solution Substances 0.000 title claims abstract description 47
- 239000011230 binding agent Substances 0.000 title claims abstract description 46
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 80
- 239000000178 monomer Substances 0.000 claims abstract description 63
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 49
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 32
- 150000001875 compounds Chemical class 0.000 claims abstract description 24
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 20
- 229920000642 polymer Polymers 0.000 claims abstract description 18
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims abstract description 14
- SNVLJLYUUXKWOJ-UHFFFAOYSA-N methylidenecarbene Chemical compound C=[C] SNVLJLYUUXKWOJ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 10
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 5
- 239000007773 negative electrode material Substances 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 12
- -1 acryl Chemical group 0.000 description 77
- 238000002360 preparation method Methods 0.000 description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 35
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 32
- 150000003839 salts Chemical class 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 23
- 239000002904 solvent Substances 0.000 description 22
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 150000007524 organic acids Chemical class 0.000 description 16
- 239000002245 particle Substances 0.000 description 16
- 229910052744 lithium Inorganic materials 0.000 description 15
- 239000000126 substance Substances 0.000 description 15
- 229910052799 carbon Inorganic materials 0.000 description 14
- 239000000839 emulsion Substances 0.000 description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 13
- 239000010408 film Substances 0.000 description 13
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 13
- 239000010410 layer Substances 0.000 description 13
- 238000003860 storage Methods 0.000 description 13
- 239000006185 dispersion Substances 0.000 description 12
- 230000014759 maintenance of location Effects 0.000 description 12
- 239000011149 active material Substances 0.000 description 11
- 239000000654 additive Substances 0.000 description 11
- 230000000996 additive effect Effects 0.000 description 11
- 229920001577 copolymer Polymers 0.000 description 11
- 150000002825 nitriles Chemical class 0.000 description 11
- 239000002131 composite material Substances 0.000 description 10
- 125000004122 cyclic group Chemical group 0.000 description 10
- 238000007599 discharging Methods 0.000 description 10
- 239000007772 electrode material Substances 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- 239000002134 carbon nanofiber Substances 0.000 description 9
- 239000011267 electrode slurry Substances 0.000 description 9
- 239000008151 electrolyte solution Substances 0.000 description 9
- 230000009477 glass transition Effects 0.000 description 9
- 229920000126 latex Polymers 0.000 description 9
- 239000004816 latex Substances 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 229910052723 transition metal Inorganic materials 0.000 description 9
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 8
- 239000003575 carbonaceous material Substances 0.000 description 8
- 125000000753 cycloalkyl group Chemical group 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 239000002210 silicon-based material Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 229910000676 Si alloy Inorganic materials 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 229920001519 homopolymer Polymers 0.000 description 7
- 239000011572 manganese Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000006386 neutralization reaction Methods 0.000 description 7
- 239000007774 positive electrode material Substances 0.000 description 7
- 229910052814 silicon oxide Inorganic materials 0.000 description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 150000001733 carboxylic acid esters Chemical class 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 229910001873 dinitrogen Inorganic materials 0.000 description 6
- 239000002270 dispersing agent Substances 0.000 description 6
- 229910017053 inorganic salt Inorganic materials 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 150000003624 transition metals Chemical class 0.000 description 6
- 229910019142 PO4 Inorganic materials 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 229910052783 alkali metal Inorganic materials 0.000 description 5
- 239000002041 carbon nanotube Substances 0.000 description 5
- 229910021393 carbon nanotube Inorganic materials 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 150000001993 dienes Chemical class 0.000 description 5
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 5
- 239000011888 foil Substances 0.000 description 5
- 238000005227 gel permeation chromatography Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 5
- 239000010452 phosphate Substances 0.000 description 5
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical class [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 5
- 239000003115 supporting electrolyte Substances 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 239000011889 copper foil Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 239000007870 radical polymerization initiator Substances 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- SZHIIIPPJJXYRY-UHFFFAOYSA-M sodium;2-methylprop-2-ene-1-sulfonate Chemical compound [Na+].CC(=C)CS([O-])(=O)=O SZHIIIPPJJXYRY-UHFFFAOYSA-M 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- GNWBLLYJQXKPIP-ZOGIJGBBSA-N (1s,3as,3bs,5ar,9ar,9bs,11as)-n,n-diethyl-6,9a,11a-trimethyl-7-oxo-2,3,3a,3b,4,5,5a,8,9,9b,10,11-dodecahydro-1h-indeno[5,4-f]quinoline-1-carboxamide Chemical compound CN([C@@H]1CC2)C(=O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H](C(=O)N(CC)CC)[C@@]2(C)CC1 GNWBLLYJQXKPIP-ZOGIJGBBSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- HFCUBKYHMMPGBY-UHFFFAOYSA-N 2-methoxyethyl prop-2-enoate Chemical compound COCCOC(=O)C=C HFCUBKYHMMPGBY-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 239000004971 Cross linker Substances 0.000 description 3
- 229910032387 LiCoO2 Inorganic materials 0.000 description 3
- 229910052493 LiFePO4 Inorganic materials 0.000 description 3
- 229910003005 LiNiO2 Inorganic materials 0.000 description 3
- 229910001290 LiPF6 Inorganic materials 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229920002125 Sokalan® Polymers 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 3
- 239000006230 acetylene black Substances 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 239000003125 aqueous solvent Substances 0.000 description 3
- 229910021383 artificial graphite Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 238000007606 doctor blade method Methods 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 239000003273 ketjen black Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 125000002950 monocyclic group Chemical group 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000004584 polyacrylic acid Substances 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- 150000003460 sulfonic acids Chemical class 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
- YXYJVFYWCLAXHO-UHFFFAOYSA-N 2-methoxyethyl 2-methylprop-2-enoate Chemical compound COCCOC(=O)C(C)=C YXYJVFYWCLAXHO-UHFFFAOYSA-N 0.000 description 2
- XCJGLBWDZKLQCY-UHFFFAOYSA-N 2-methylpropane-2-sulfonic acid Chemical compound CC(C)(C)S(O)(=O)=O XCJGLBWDZKLQCY-UHFFFAOYSA-N 0.000 description 2
- JJYPMNFTHPTTDI-UHFFFAOYSA-N 3-methylaniline Chemical compound CC1=CC=CC(N)=C1 JJYPMNFTHPTTDI-UHFFFAOYSA-N 0.000 description 2
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 2
- NUXLDNTZFXDNBA-UHFFFAOYSA-N 6-bromo-2-methyl-4h-1,4-benzoxazin-3-one Chemical compound C1=C(Br)C=C2NC(=O)C(C)OC2=C1 NUXLDNTZFXDNBA-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 229910001558 CF3SO3Li Inorganic materials 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 229910012735 LiCo1/3Ni1/3Mn1/3O2 Inorganic materials 0.000 description 2
- 229910002993 LiMnO2 Inorganic materials 0.000 description 2
- 229910014395 LiNi1/2Mn3/2O4 Inorganic materials 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 229910001069 Ti alloy Inorganic materials 0.000 description 2
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 description 2
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- QUKGYYKBILRGFE-UHFFFAOYSA-N benzyl acetate Chemical compound CC(=O)OCC1=CC=CC=C1 QUKGYYKBILRGFE-UHFFFAOYSA-N 0.000 description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 150000005678 chain carbonates Chemical class 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 150000005676 cyclic carbonates Chemical class 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229960001484 edetic acid Drugs 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 239000006232 furnace black Substances 0.000 description 2
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- PQLMXFQTAMDXIZ-UHFFFAOYSA-N isoamyl butyrate Chemical compound CCCC(=O)OCCC(C)C PQLMXFQTAMDXIZ-UHFFFAOYSA-N 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- 150000002641 lithium Chemical group 0.000 description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 239000002931 mesocarbon microbead Substances 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 2
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 2
- RNVCVTLRINQCPJ-UHFFFAOYSA-N o-toluidine Chemical compound CC1=CC=CC=C1N RNVCVTLRINQCPJ-UHFFFAOYSA-N 0.000 description 2
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 2
- 150000003016 phosphoric acids Chemical class 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- NMRPBPVERJPACX-UHFFFAOYSA-N (3S)-octan-3-ol Natural products CCCCCC(O)CC NMRPBPVERJPACX-UHFFFAOYSA-N 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 description 1
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N 1,4-Benzenediol Natural products OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 1
- 125000004066 1-hydroxyethyl group Chemical group [H]OC([H])([*])C([H])([H])[H] 0.000 description 1
- JQCSUVJDBHJKNG-UHFFFAOYSA-N 1-methoxy-ethyl Chemical group C[CH]OC JQCSUVJDBHJKNG-UHFFFAOYSA-N 0.000 description 1
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- WOFPPJOZXUTRAU-UHFFFAOYSA-N 2-Ethyl-1-hexanol Natural products CCCCC(O)CCC WOFPPJOZXUTRAU-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- FCYVWWWTHPPJII-UHFFFAOYSA-N 2-methylidenepropanedinitrile Chemical compound N#CC(=C)C#N FCYVWWWTHPPJII-UHFFFAOYSA-N 0.000 description 1
- AUZRCMMVHXRSGT-UHFFFAOYSA-N 2-methylpropane-1-sulfonic acid;prop-2-enamide Chemical compound NC(=O)C=C.CC(C)CS(O)(=O)=O AUZRCMMVHXRSGT-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- MBNVSWHUJDDZRH-UHFFFAOYSA-N 2-methylthiirane Chemical compound CC1CS1 MBNVSWHUJDDZRH-UHFFFAOYSA-N 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 description 1
- DSMUTQTWFHVVGQ-UHFFFAOYSA-N 4,5-difluoro-1,3-dioxolan-2-one Chemical compound FC1OC(=O)OC1F DSMUTQTWFHVVGQ-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- BJWMSGRKJIOCNR-UHFFFAOYSA-N 4-ethenyl-1,3-dioxolan-2-one Chemical compound C=CC1COC(=O)O1 BJWMSGRKJIOCNR-UHFFFAOYSA-N 0.000 description 1
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 1
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
- LPEKGGXMPWTOCB-UHFFFAOYSA-N 8beta-(2,3-epoxy-2-methylbutyryloxy)-14-acetoxytithifolin Natural products COC(=O)C(C)O LPEKGGXMPWTOCB-UHFFFAOYSA-N 0.000 description 1
- 229920003026 Acene Polymers 0.000 description 1
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- MRABAEUHTLLEML-UHFFFAOYSA-N Butyl lactate Chemical compound CCCCOC(=O)C(C)O MRABAEUHTLLEML-UHFFFAOYSA-N 0.000 description 1
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229910018029 Cu2V2O3 Inorganic materials 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910016861 F9SO3 Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910002986 Li4Ti5O12 Inorganic materials 0.000 description 1
- 229910010584 LiFeO2 Inorganic materials 0.000 description 1
- 229910010756 LiFeVO4 Inorganic materials 0.000 description 1
- 229910012752 LiNi0.5Mn0.5O2 Inorganic materials 0.000 description 1
- 229910015915 LiNi0.8Co0.2O2 Inorganic materials 0.000 description 1
- 229910016618 LixFe2(SO4)3 Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methyl-N-phenylamine Natural products CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 1
- 229910003827 NRaRb Inorganic materials 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229910002790 Si2N2O Inorganic materials 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 229910003092 TiS2 Inorganic materials 0.000 description 1
- 229910010322 TiS3 Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 description 1
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 1
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 description 1
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 description 1
- ZYXUQEDFWHDILZ-UHFFFAOYSA-N [Ni].[Mn].[Li] Chemical compound [Ni].[Mn].[Li] ZYXUQEDFWHDILZ-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 1
- 239000000783 alginic acid Substances 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 229960001126 alginic acid Drugs 0.000 description 1
- 150000004781 alginic acids Chemical class 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000001463 antimony compounds Chemical class 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 150000001495 arsenic compounds Chemical class 0.000 description 1
- 229940007550 benzyl acetate Drugs 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- KLIYQWXIWMRMGR-UHFFFAOYSA-N buta-1,3-diene;methyl 2-methylprop-2-enoate Chemical compound C=CC=C.COC(=O)C(C)=C KLIYQWXIWMRMGR-UHFFFAOYSA-N 0.000 description 1
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 1
- 239000001191 butyl (2R)-2-hydroxypropanoate Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 239000006231 channel black Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- CKFRRHLHAJZIIN-UHFFFAOYSA-N cobalt lithium Chemical compound [Li].[Co] CKFRRHLHAJZIIN-UHFFFAOYSA-N 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- ODQWQRRAPPTVAG-GZTJUZNOSA-N doxepin Chemical compound C1OC2=CC=CC=C2C(=C/CCN(C)C)/C2=CC=CC=C21 ODQWQRRAPPTVAG-GZTJUZNOSA-N 0.000 description 1
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- QHSJIZLJUFMIFP-UHFFFAOYSA-N ethene;1,1,2,2-tetrafluoroethene Chemical group C=C.FC(F)=C(F)F QHSJIZLJUFMIFP-UHFFFAOYSA-N 0.000 description 1
- HDERJYVLTPVNRI-UHFFFAOYSA-N ethene;ethenyl acetate Chemical group C=C.CC(=O)OC=C HDERJYVLTPVNRI-UHFFFAOYSA-N 0.000 description 1
- BNKAXGCRDYRABM-UHFFFAOYSA-N ethenyl dihydrogen phosphate Chemical compound OP(O)(=O)OC=C BNKAXGCRDYRABM-UHFFFAOYSA-N 0.000 description 1
- BPFOYPDHLJUICH-UHFFFAOYSA-N ethenyl ethyl carbonate Chemical compound CCOC(=O)OC=C BPFOYPDHLJUICH-UHFFFAOYSA-N 0.000 description 1
- 125000005745 ethoxymethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])* 0.000 description 1
- 229940116333 ethyl lactate Drugs 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- AHAREKHAZNPPMI-UHFFFAOYSA-N hexa-1,3-diene Chemical compound CCC=CC=C AHAREKHAZNPPMI-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 229920003049 isoprene rubber Polymers 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000006233 lamp black Substances 0.000 description 1
- 150000002611 lead compounds Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001547 lithium hexafluoroantimonate(V) Inorganic materials 0.000 description 1
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 description 1
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 description 1
- 229910001537 lithium tetrachloroaluminate Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- SWAIALBIBWIKKQ-UHFFFAOYSA-N lithium titanium Chemical compound [Li].[Ti] SWAIALBIBWIKKQ-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- FSQQTNAZHBEJLS-UPHRSURJSA-N maleamic acid Chemical compound NC(=O)\C=C/C(O)=O FSQQTNAZHBEJLS-UPHRSURJSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000008268 mayonnaise Substances 0.000 description 1
- 235000010746 mayonnaise Nutrition 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 1
- 229940117841 methacrylic acid copolymer Drugs 0.000 description 1
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- 229940057867 methyl lactate Drugs 0.000 description 1
- XTBFPVLHGVYOQH-UHFFFAOYSA-N methyl phenyl carbonate Chemical compound COC(=O)OC1=CC=CC=C1 XTBFPVLHGVYOQH-UHFFFAOYSA-N 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- 229910052961 molybdenite Inorganic materials 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 229940094933 n-dodecane Drugs 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000002116 nanohorn Substances 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002868 norbornyl group Chemical group C12(CCC(CC1)C2)* 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- MHYFEEDKONKGEB-UHFFFAOYSA-N oxathiane 2,2-dioxide Chemical compound O=S1(=O)CCCCO1 MHYFEEDKONKGEB-UHFFFAOYSA-N 0.000 description 1
- 239000001254 oxidized starch Substances 0.000 description 1
- 235000013808 oxidized starch Nutrition 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- MTZWHHIREPJPTG-UHFFFAOYSA-N phorone Chemical compound CC(C)=CC(=O)C=C(C)C MTZWHHIREPJPTG-UHFFFAOYSA-N 0.000 description 1
- 229930193351 phorone Natural products 0.000 description 1
- 239000008363 phosphate buffer Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 125000005767 propoxymethyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])[#8]C([H])([H])* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 229910052705 radium Inorganic materials 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007717 redox polymerization reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910021484 silicon-nickel alloy Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000006234 thermal black Substances 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- VOVUARRWDCVURC-UHFFFAOYSA-N thiirane Chemical compound C1CS1 VOVUARRWDCVURC-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 229910000319 transition metal phosphate Inorganic materials 0.000 description 1
- 229910000385 transition metal sulfate Inorganic materials 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- ZTWTYVWXUKTLCP-UHFFFAOYSA-N vinylphosphonic acid Chemical compound OP(O)(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-N 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0416—Methods of deposition of the material involving impregnation with a solution, dispersion, paste or dry powder
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the disclosure relates to a binder aqueous solution for a lithium-ion battery, a slurry for a lithium-ion battery negative electrode, a negative electrode for a lithium-ion battery, and a lithium-ion battery.
- Lithium-ion batteries have a small size, light weight and high energy density, and further, are repeatedly chargeable and dischargeable, and are used in a wide range of applications. Hence, in recent years, improvements to battery members such as electrodes have been studied with the aim of improving the performance of lithium-ion batteries.
- the positive electrode and negative electrode of a lithium-ion battery are both produced in the following manner.
- a slurry prepared by dispersing an electrode active material and a binder resin in a solvent is applied on both sides of a current collector (for example, a metal foil), and after the solvent is dried and removed to form an electrode layer, the resultant is compression-molded by a roll press machine or the like.
- Patent Documents 1 and 2 As a binder of a water-soluble resin.
- Patent Document 3 With respect to expansion and contraction of an active material associated with charging and discharging, it has been proposed to suppress the expansion by adding a crosslinker to a particulate resin being a binder resin.
- the crosslinker usually causes a crosslinking reaction in the drying step after the slurry composition is applied to the current collector, and forms crosslinks between particles of the particulate resin or the like.
- problems to be solved by the disclosure include to provide a binder aqueous solution for a lithium-ion battery, the binder aqueous solution imparting a good discharge capacity retention rate to a lithium-ion battery, good electrode flexibility and electrode adhesion to an electrode, and good storage stability to a slurry.
- the binder aqueous solution for a lithium-ion battery according to the disclosure is capable of imparting excellent storage stability to a slurry for a lithium-ion battery negative electrode.
- the slurry for a lithium-ion battery negative electrode according to the disclosure has excellent storage stability.
- the electrode according to the disclosure has excellent flexibility and adhesion.
- the battery according to the disclosure has an excellent discharge capacity retention rate.
- ranges of numerical values such as physical property values and content may be suitably set (for example, selected from the upper and lower limit values described in each item below).
- the numerical value ⁇ is in a range of, for example, A4 or less, A3 or less, A2 or less, A1 or more, A2 or more, A3 or more, A1 to A2, A1 to A3, A1 to A4, A2 to A3, A2 to A4, and A3 to A4.
- Aqueous Solution for Lithium-ion Battery
- water-soluble means having an insoluble content of less than 0.5% by mass (less than 2.5 mg) when 0.5 g of a compound thereof is dissolved in 100 g of water at 25 °C.
- the component (A) is not water-soluble, since it does not dissolve in water, no aqueous solution is formed at all. As a result, the component (A) does not contribute to dispersion of the slurry. In addition, viscosity required for application of the slurry to a current collector cannot be imparted to the slurry.
- the insoluble content of the component (A) is, for example, less than 0.5% by mass, less than 0.4% by mass, less than 0.3% by mass, less than 0.2% by mass, less than 0.1% by mass, or 0% by mass.
- poly(meth)acrylamide means a (co)polymer obtained by polymerizing a monomer group containing a (meth)acrylamide group-containing compound.
- (meth)acryl means “at least one selected from the group consisting of acryl and methacryl.”
- (meth)acrylate means “at least one selected from the group consisting of acrylate and methacrylate.”
- (Meth)acryloyl means “at least one selected from the group consisting of acryloyl and methacryloyl.”
- (meth)acrylamide group-containing compound means a compound having a (meth)acrylamide group.
- the (meth)acrylamide group-containing compound various known ones may be used without particular limitation, and may be used singly or in combination of two or more.
- the (meth)acrylamide group-containing compound is expressed by the following structural formula: (In the formula, R 1 is a hydrogen atom or a methyl group; R 2 and R 3 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, or an acetyl group, or a group in which R 2 and R 3 form a ring structure together; R 4 and R 5 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a hydroxy group, an amino group (-NR a R b (in which R a and R b are each independently a hydrogen atom or a substituted or unsubstituted alkyl group), or an acetyl group. Examples of a substituent of the substituted alkyl group include hydroxy group, amino group, and acetyl group. In addition, examples of the group in which R 2 and R 3 form a ring structure together include morpholyl group.)
- alkyl group examples include linear alkyl group, branched alkyl group, and cycloalkyl group.
- the linear alkyl group is expressed by a general formula of -C n H 2n+1 (in which n is an integer of 1 or more).
- Examples of the linear alkyl group include methyl group, ethyl group, propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, and n-decamethyl group.
- the branched alkyl group is a group in which at least one hydrogen of a linear alkyl group is substituted with an alkyl group.
- Examples of the branched alkyl group include i-propyl group, i-butyl group, s-butyl group, t-butyl group, diethylpentyl group, trimethylbutyl group, trimethylpentyl group, and trimethylhexyl group.
- cycloalkyl group examples include monocyclic cycloalkyl group, crosslinked cyclic cycloalkyl group, and condensed cyclic cycloalkyl group.
- monocyclic means having a cyclic structure formed by covalent bonding of carbons and without crosslinking structure therein.
- Condensed cyclic means having a cyclic structure in which two or more single rings share two atoms (that is, only one side of each ring is shared (condensed) with each other).
- Crosslinked cyclic means having a cyclic structure in which two or more single rings share three or more atoms.
- Examples of the monocyclic cycloalkyl group include cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclodecyl group, and 3,5,5-trimethylcyclohexyl group.
- crosslinked cyclic cycloalkyl group examples include tricyclodecyl group, adamantyl group, and norbornyl group.
- Examples of the condensed cyclic cycloalkyl group include bicyclodecyl group.
- Examples of the above (meth)acrylamide group-containing compound (a) include (meth)acrylamide, N-isopropyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N,N-dimethylaminopropyl(meth)acrylamide, N-methylol(meth)acrylamide, diacetone(meth)acrylamide, maleic acid amide, (meth)acrylamide t-butylsulfonic acid, (meth)acryloylmorpholine, hydroxyethyl(meth)acrylamide, and a salt thereof.
- Examples of the above salt include dimethylaminopropyl(meth)acrylamide methyl chloride quaternary salt, and dimethylaminoethyl (meth)acrylate benzyl chloride quaternary salt.
- (meth)acrylamide especially acrylamide when used, a binder can be prepared which has high water solubility, has a high interaction with an electrode active material, and improves slurry dispersibility or a binding property between electrode active materials inside an electrode.
- the upper limit and lower limit of the content of the (meth)acrylamide group-containing compound with respect to 100 mol% of the monomer group are, for example, 95 mol%, 90 mol%, 85 mol%, 80 mol%, 75 mol%, 70 mol%, 65 mol%, 60 mol%, 55 mol%, 50 mol%, 45 mol%, 40 mol%, 35 mol%, and 30 mol%.
- the above content preferably ranges from 30 mol% to 95 mol%.
- the upper limit and lower limit of the content of the (meth)acrylamide group-containing compound with respect to 100% by mass of the monomer group are, for example, 95% by mass, 90% by mass, 85% by mass, 80% by mass, 75% by mass, 70% by mass, 65% by mass, 60% by mass, 55% by mass, 50% by mass, 45% by mass, 40% by mass, 35% by mass, 30% by mass, 25% by mass, and 20% by mass.
- the content of the (meth)acrylamide group-containing compound with respect to 100% by mass of the monomer group is preferably 20% by mass to 95% by mass.
- R 1 is a hydrogen atom or a methyl group
- R 2 is an alkylene group having 1 to 4 carbon atoms
- R 3 is an alkyl group having 1 to 4 carbon atoms
- a total number of carbon atoms of the groups R 1 , R 2 and R 3 is 5 or less.
- alkoxyalkyl (meth)acrylate various known ones may be used without particular limitation, and may be used singly or in combination of two or more.
- the upper limit and lower limit of the total number of carbon atoms of the groups R 1 , R 2 and R 3 are, for example, 5, 4, 3, and 2.
- the total number of carbon atoms of the groups R 1 , R 2 and R 3 is defined as 5 or less from the viewpoints of ensuring the water solubility and the availability of the component (A). The reason is that, when the total number of carbon atoms exceeds 5, the water solubility of the alkoxyalkyl (meth)acrylate decreases and it is difficult to ensure the water solubility of the component (A).
- the above number of carbon atoms is more preferably 4 or less.
- the number of carbon atoms of R 3 is preferably 1.
- a monomer in which the total number of carbon atoms of the groups R 1 , R 2 and R 3 in general formula (1) exceeds 5 is a hydrophobic monomer.
- the component (A) is produced using such a hydrophobic monomer, the water solubility of the component (A) decreases.
- surface tension of an aqueous solution containing the component (A) decreases.
- bubbles are likely to be generated. If the bubbles are generated, the following problems may occur.
- Combinations of the groups R 1 , R 2 and R 3 are exemplified as follows. [Table 1] -R 1 -R 2 - -R 3 Total number of carbon atoms of groups R 1 , R 2 and R 3 -H -CH 2 - -Me 2 -H -CH 2 - -CH 2 Me 3 -H -CH 2 - -CH 2 CH 2 Me 4 -H -CH 2 - -CH(Me) 2 4 -H -CH 2 - -CH 2 CH 2 CH 2 Me 5 -H -CH 2 - -CH(Me)CH 2 CH 3 5 -H -CH 2 - -CH 2 CH(Me) 2 5 -H -CH 2 - -C(Me) 3 5 -H -CH 2 CH 2 - -CH 3 3 -H -CH(Me)- -CH 3 3 -H -CH(Me)- -CH 3 3 -H -
- alkoxyalkyl (meth)acrylate examples include methoxymethyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 1-methoxyethyl (meth)acrylate, 3-methoxypropyl (meth)acrylate, 2-methoxypropyl (meth)acrylate, 1-methoxypropyl (meth)acrylate, 4-methoxybutyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, 2-methoxybutyl (meth)acrylate, 1-methoxybutyl (meth)acrylate, ethoxymethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 1-ethoxyethyl (meth)acrylate, 3-ethoxypropyl (meth)acrylate, 2-ethoxypropyl (meth)acrylate, 1-ethoxypropyl (meth)acrylate, propoxymethyl (meth)acrylate, 2-propoxyeth)acryl
- the upper limit and lower limit of the content of the above alkoxyalkyl (meth)acrylate with respect to 100 mol% of the monomer group are, for example, 40 mol%, 35 mol%, 30 mol%, 25 mol%, 20 mol%, 15 mol%, 10 mol%, 9 mol%, and 5 mol%. In one embodiment, the above content preferably ranges from 5 mol% to 40 mol%.
- the upper limit and lower limit of the content of the above alkoxyalkyl (meth)acrylate with respect to 100% by mass of the monomer group are, for example, 60% by mass, 55% by mass, 50% by mass, 45% by mass, 40% by mass, 35% by mass, 30% by mass, 25% by mass, 20% by mass, 15% by mass, 10% by mass, and 5% by mass.
- the content of the above alkoxyalkyl (meth)acrylate with respect to 100% by mass of the monomer group is preferably 5% by mass to 60% by mass.
- an unsaturated organic acid means a compound having an acidic group and a polymerizable unsaturated bond.
- the unsaturated organic acid may be used singly or in combination of two or more.
- a salt of an unsaturated organic acid means a salt of the above unsaturated organic acid.
- the salt of the unsaturated organic acid may be used singly or in combination of two or more.
- Examples of the unsaturated organic acid include unsaturated carboxylic acid, unsaturated sulfonic acid, and unsaturated phosphoric acid.
- Examples of the unsaturated carboxylic acid include (meth)acrylic acid, crotonic acid, maleic acid, fumaric acid, and itaconic acid.
- Examples of the unsaturated sulfonic acid include: ⁇ , ⁇ -ethylenically unsaturated sulfonic acid, such as vinylsulfonic acid, styrenesulfonic acid, and (meth)allylsulfonic acid; (meth)acrylamide t-butylsulfonic acid, 2-(meth)acrylamide-2-methylpropanesulfonic acid, 2-(meth)acrylamide-2-hydroxypropanesulfonic acid, 3-sulfopropane(meth)acrylic ester, and bis-(3-sulfopropyl)itaconic ester.
- ⁇ , ⁇ -ethylenically unsaturated sulfonic acid such as vinylsulfonic acid, styrenesulfonic acid, and (meth)allylsulfonic acid
- (meth)acrylamide t-butylsulfonic acid 2-(meth)acrylamide-2-methylpropanesulfonic acid, 2-(me
- Examples of the unsaturated phosphoric acid include vinylphosphonic acid, vinyl phosphate, bis((meth)acryloxyethyl) phosphate, diphenyl-2-(meth)acryloyloxyethyl phosphate, dibutyl-2-(meth)acryloyloxyethyl phosphate, dioctyl-2-(meth)acryloyloxyethyl phosphate, monomethyl-2-(meth)acryloyloxyethyl phosphate, and 3-(meth)acryloxy-2-hydroxypropanephosphoric acid.
- a compound corresponding to both a (meth)acrylamide group-containing compound and an unsaturated organic acid is regarded as an unsaturated organic acid.
- Examples of a salt of an unsaturated organic acid include an inorganic salt of an unsaturated organic acid.
- An inorganic salt of an unsaturated organic acid refers to a salt whose cationic portion is a metal cation.
- Examples of an inorganic salt include alkali metal salt and alkaline earth metal salt.
- alkali metal examples include lithium, sodium, and potassium.
- alkaline earth metal examples include magnesium and calcium.
- the upper limit and lower limit of the content of the unsaturated organic acid or a salt thereof with respect to 100 mol% of the monomer group are, for example, 40 mol%, 35 mol%, 30 mol%, 25 mol%, 20 mol%, 15 mol%, 10 mol%, 5 mol%, and 0 mol%.
- the above content is preferably 0 mol% to 40 mol %, and more preferably 10 mol% to 40 mol% from the viewpoint of improving the water solubility and slurry dispersibility of the component (A).
- the upper limit and lower limit of the content of the unsaturated organic acid or a salt thereof with respect to 100% by mass of the monomer group are, for example, 50% by mass, 45% by mass, 40% by mass, 35% by mass, 30% by mass, 25% by mass, 20% by mass, 15% by mass, 10% by mass, 5% by mass, and 0% by mass.
- the content of the unsaturated organic acid or a salt thereof with respect to 100% by mass of the monomer group is preferably 0% by mass to 50% by mass.
- various known ones may be used without particular limitation, and may be used singly or in combination of two or more.
- hydroxyalkyl group having 2 to 4 carbon atoms refers to a group in which one of hydrogen atoms constituting an alkyl group having 2 to 4 carbon atoms is substituted with a hydroxy group.
- Examples of the hydroxyalkyl(meth)acrylate having a hydroxyalkyl group having 2 to 4 carbon atoms include 1-hydroxyethyl(meth)acrylate, 2-hydroxyethyl(meth)acrylate, 1-hydroxypropyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate, 3-hydroxypropyl(meth)acrylate, 2-hydroxy-1-methylethyl(meth)acrylate, 1-hydroxy-2-methylethyl(meth)acrylate, 1-hydroxybutyl(meth)acrylate, 2-hydroxybutyl(meth)acrylate, 3-hydroxybutyl(meth)acrylate, 4-hydroxybutyl(meth)acrylate, 1-hydroxy-1-methyl-propyl(meth)acrylate, 2-hydroxy- 1-methyl-propyl(meth)acrylate, 3-hydroxy-1-methyl-propyl(meth)acrylate, 1-ethyl-2-hydroxyethyl(meth)acrylate, 1-hydroxy-2-methyl-propyl(meth)
- the upper limit and lower limit of the content of the hydroxyalkyl(meth)acrylate having a hydroxyalkyl group having 2 to 4 carbon atoms with respect to 100 mol% of the monomer group are, for example, 40 mol%, 35 mol%, 30 mol%, 25 mol%, 20 mol%, 15 mol%, 10 mol%, 5 mol%, and 0 mol%.
- the above content is preferably 0 mol% to 40 mol %, and more preferably 5 mol% to 40 mol% from the viewpoint of improving the water solubility and electrode flexibility of the component (A).
- the upper limit and lower limit of the content of the hydroxyalkyl(meth)acrylate having a hydroxyalkyl group having 2 to 4 carbon atoms with respect to 100% by mass of the monomer group are, for example, 40% by mass, 35% by mass, 30% by mass, 25% by mass, 20% by mass, 15% by mass, 10% by mass, 5% by mass, and 0% by mass.
- the content of the hydroxyalkyl(meth)acrylate (d) having hydroxyalkyl group having 2 to 4 carbon atoms with respect to 100% by mass of the monomer group is preferably 0% by mass to 40% by mass.
- An ⁇ , ⁇ -unsaturated nitrile may be used singly or in combination of two or more.
- the ⁇ , ⁇ -unsaturated nitrile can be suitably used for the purpose of imparting flexibility to an electrode.
- Examples of the ⁇ , ⁇ -unsaturated nitrile include (meth)acrylonitrile, ⁇ -chloro(meth)acrylonitrile, ⁇ -ethyl(meth)acrylonitrile, and vinylidene cyanide. Among them, (meth)acrylonitrile is preferable, and acrylonitrile is particularly preferable.
- the upper limit and lower limit of the content of the ⁇ , ⁇ -unsaturated nitrile with respect to 100 mol% of the monomer group are, for example, 40 mol%, 35 mol%, 30 mol%, 25 mol%, 20 mol%, 15 mol%, 10 mol%, 5 mol%, and 0 mol%.
- the above content is preferably 0 mol% to 40 mol %, and more preferably 5 mol% to 40 mol% from the viewpoint of improving the electrode flexibility.
- the upper limit and lower limit of the content of the ⁇ , ⁇ -unsaturated nitrile with respect to 100 % by mass of the monomer group are exemplified by 30% by mass, 25% by mass, 20% by mass, 15% by mass, 10% by mass, 5% by mass, and 0% by mass.
- the content of the ⁇ , ⁇ -unsaturated nitrile (e) with respect to 100% by mass of the monomer group is preferably 0% by mass to 30% by mass.
- the upper limit and lower limit of a molar ratio [amount of substance of component (b) / amount of substance of component (a)] between the component (b) and the component (a) contained in the monomer group are, for example, 1.3, 1, 0.9, 0.5, 0.2, 0.1, 0.09, and 0.05. In one embodiment, the above molar ratio is preferably 0.05 to 1.3.
- the upper limit and lower limit of a molar ratio [amount of substance of any one of the components (c) to (e) / amount of substance of component (a)] between any one of the components (c) to (e) and the component (a) contained in the monomer group are, for example, 1.3, 1, 0.9, 0.5, 0.2, 0.1, 0.09, 0.05 and 0.
- the above molar ratio is preferably 0 to 1.3.
- the upper limit and lower limit of a molar ratio [amount of substance of any one of the components (c) to (e) / amount of substance of component (b)] between any one of the components (c) to (e) and the component (b) contained in the monomer group are, for example, 8, 7, 6, 5, 4, 3, 2, 1, 0.9, 0.5, 0.2, 0.1, 0.09, 0.05, and 0.
- the above molar ratio is preferably 0 to 8.
- the upper limit and lower limit of a mass ratio [mass of component (b) / mass of component (a)] between the component (b) and the component (a) contained in the monomer group are, for example, 3, 2.5, 2, 1.5, 1, 0.9, 0.5, 0.2, 0.1, 0.09, and 0.05. In one embodiment, the above mass ratio is preferably 0.05 to 3.
- the upper limit and lower limit of a mass ratio [mass of component (c) / mass of component (a)] between the component (c) and the component (a) contained in the monomer group are, for example, 2.5, 2, 1.5, 1, 0.9, 0.5, 0.2, 0.1, 0.09, 0.05, and 0. In one embodiment, the above mass ratio is preferably 0 to 2.5.
- the upper limit and lower limit of a mass ratio [mass of component (d) / mass of component (a)] between the component (d) and the component (a) contained in the monomer group are, for example, 2, 1.5, 1, 0.9, 0.5, 0.2, 0.1, 0.09, 0.05, and 0. In one embodiment, the above mass ratio is preferably 0 to 2.
- the upper limit and lower limit of a mass ratio [mass of component (e) / mass of component (a)] between the component (e) and the component (a) contained in the monomer group are, for example, 1.5, 1, 0.9, 0.5, 0.2, 0.1, 0.09, 0.05, and 0. In one embodiment, the above mass ratio is preferably 0 to 1.5.
- the upper limit and lower limit of a mass ratio [mass of component (c) / mass of component (b)] between the component (c) and the component (b) contained in the monomer group are, for example, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1.5, 1, 0.9, 0.5, 0.2, 0.1, 0.09, 0.05, and 0.
- the above mass ratio is preferably 0 to 10.
- the upper limit and lower limit of a mass ratio [mass of component (d) / mass of component (b)] between the component (d) and the component (b) contained in the monomer group are, for example, 8, 7, 6, 5, 4, 3, 2, 1.5, 1, 0.9, 0.5, 0.2, 0.1, 0.09, 0.05, and 0. In one embodiment, the above mass ratio is preferably 0 to 8.
- the upper limit and lower limit of a mass ratio [mass of component (e) / mass of component (b)] between the component (e) and the component (b) contained in the monomer group are, for example, 6, 5, 4, 3, 2, 1.5, 1, 0.9, 0.5, 0.2, 0.1, 0.09, 0.05, and 0. In one embodiment, the above mass ratio is preferably 0 to 6.
- monomers (other components) that correspond to none of the components (a) to (e) may be used as long as the desired effects of the disclosure are not impaired.
- various known ones may be used singly or in combination of two or more.
- Examples of the other components include a hydroxyl group-free unsaturated carboxylic ester, a conjugated diene, and an aromatic vinyl compound.
- the hydroxyl group-free unsaturated carboxylic ester is preferably a hydroxyl group-free (meth)acrylic ester.
- the hydroxyl group-free (meth)acrylic ester include a hydroxyl group-free linear (meth)acrylic ester, a hydroxyl group-free branched (meth)acrylic ester, a hydroxyl group-free alicyclic (meth)acrylic ester, and a hydroxyl group-free substituted (meth)acrylic ester.
- hydroxyl group-free linear (meth)acrylic ester examples include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, n-amyl (meth)acrylate, hexyl (meth)acrylate, n-octyl (meth)acrylate, nonyl (meth)acrylate, and decyl (meth)acrylate.
- hydroxyl group-free branched (meth)acrylic ester examples include i-propyl (meth)acrylate, i-butyl (meth)acrylate, i-amyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate.
- hydroxyl group-free alicyclic (meth)acrylic ester examples include cyclohexyl (meth)acrylate.
- hydroxyl group-free substituted (meth)acrylic ester examples include glycidyl (meth)acrylate, allyl (meth)acrylate, and ethylene di(meth)acrylate.
- the above hydroxyl group-free substituted (meth)acrylic ester also includes an alkoxyalkyl (meth)acrylate other than the above alkoxyalkyl (meth)acrylate represented by general formula (1).
- the hydroxyl group-free unsaturated carboxylic ester can be suitably used for the purpose of imparting flexibility to an electrode.
- the content of the hydroxyl group-free unsaturated carboxylic ester with respect to 100 mol% of the above monomer group is preferably less than 40 mol% (for example, less than 30 mol%, less than 20 mol%, less than 19 mol%, less than 15 mol%, less than 10 mol%, less than 5 mol%, less than 1 mol%, or 0 mol%).
- the content of the hydroxyl group-free unsaturated carboxylic ester with respect to 100% by mass of the above monomer group is preferably 40% by mass or less (for example, less than 30% by mass, less than 20% by mass, less than 19% by mass, less than 15% by mass, less than 10% by mass, less than 5% by mass, less than 1% by mass, or 0% by mass).
- conjugated diene examples include 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-chloro-1,3-butadiene, a substituted linear conjugated pentadiene, and a substituted and side chain conjugated hexadiene.
- the content of the conjugated diene with respect to 100 mol% of the above monomer group is preferably less than 10 mol%, more preferably 0 mol%.
- the upper limit and lower limit of the content of the conjugated diene with respect to 100% by mass of the above monomer group are, for example, 30% by mass, 20% by mass, 10% by mass, 5% by mass, 1% by mass, and 0% by mass. In one embodiment, the above content is preferably 0% by mass to 30% by mass.
- examples of the aromatic vinyl compound include styrene, ⁇ -methylstyrene, p-methylstyrene, vinyltoluene, chlorostyrene, and divinylbenzene.
- the content of the aromatic vinyl compound with respect to 100 mol% of the above monomer group is preferably less than 10 mol%, more preferably 0 mol%.
- the upper limit and lower limit of the content of the aromatic vinyl compound with respect to 100% by mass of the above monomer group are, for example, 30% by mass, 20% by mass, 10% by mass, 5% by mass, 1% by mass, and 0% by mass. In one embodiment, the above content is preferably 0% by mass to 30% by mass.
- a ratio of the other components than the hydroxyl group-free unsaturated carboxylic ester, the conjugated diene and the aromatic vinyl compound mentioned above in the above monomer group is, for example, less than 10 mol%, less than 5 mol%, less than 2 mol%, less than 1 mol%, less than 0.1 mol%, less than 0.01 mol%, or 0 mol%, with respect to 100 mol% of the above monomer group.
- the ratio of the other components is, for example, less than 10% by mass, less than 9% by mass, less than 7% by mass, less than 5% by mass, less than 4% by mass, less than 2% by mass, less than 1% by mass, less than 0.9% by mass, less than 0.5% by mass, less than 0.3% by mass, less than 0.1% by mass, less than 0.05% by mass, less than 0.01% by mass, or 0% by mass.
- the component (A) may be synthesized by various known polymerization methods, preferably a radical polymerization method. Specifically, it is preferable to add a radical polymerization initiator and, if necessary, a chain transfer agent, to a monomer mixture containing the aforementioned components, and, while stirring the mixture, perform a polymerization reaction at a reaction temperature of 50 °C to 100 °C.
- the reaction time is not particularly limited and is preferably 1 hour to 10 hours.
- radical polymerization initiator various known ones may be used without particular limitation.
- examples of the radical polymerization initiator include: a persulfate, such as potassium persulfate and ammonium persulfate; a redox polymerization initiator in which the above persulfate and a reductant such as sodium bisulfite are combined; and an azo initiator, such as 2,2'-azobis-2-amidinopropane dihydrochloride.
- the amount of the radical polymerization initiator used is not particularly limited, and is preferably 0.05% by mass to 5.0% by mass, more preferably 0.1% by mass to 3.0% by mass, with respect to 100% by mass of the monomer group that provides the component (A).
- the pH of a reaction solution may be adjusted by a general neutralizer such as ammonia or organic amine, potassium hydroxide, sodium hydroxide, and lithium hydroxide.
- a general neutralizer such as ammonia or organic amine, potassium hydroxide, sodium hydroxide, and lithium hydroxide.
- the pH is preferably 2 to 11.
- EDTA ethylene diamine tetraacetic acid
- the component (A) has an acid group, it can be used by a neutralization ratio thereof being appropriately adjusted (a neutralization ratio of 100% indicating that neutralization is performed by an alkali having the same number of moles as the acid component contained in the component (A); a neutralization ratio of 50% indicating that neutralization is performed by an alkali having half the number of moles of the acid component contained in the component (A)) depending on the use.
- the neutralization ratio when the electrode active material is dispersed is not particularly limited. In one embodiment, the neutralization ratio is preferably 95% to 100% after formation of a coating layer or the like. 95% or more is preferable from the viewpoint of preventing a decrease in initial capacity, and 100% or less is preferable from the viewpoint of preventing hydrolysis.
- a neutralized salt include Li salt, Na salt, K salt, ammonium salt, Mg salt, Ca salt, Zn salt, and Al salt.
- the component (A) is preferably an inorganic salt.
- the inorganic salt as the component (A) refers to a salt whose cationic portion is a metal cation. Examples of the inorganic salt include those mentioned above.
- the upper limit and lower limit of a glass transition temperature of the component (A) are, for example, 160 °C, 155 °C, 150 °C, 145 °C, 140 °C, 135 °C, 130 °C, 125 °C, 120 °C, 115 °C, 110 °C, 105 °C, 100 °C, 95 °C, 90 °C, 85 °C, 80 °C, 75 °C, 70 °C, 65 °C, 60 °C, 55 °C, 50 °C, 45 °C, 40 °C, 35 °C, 30 °C, 25 °C, 20 °C, 15 °C, 10 °C, 5 °C, and 0 °C. In one embodiment, 0 °C or higher is preferable, and 30 °C or higher is more preferable from the viewpoints of mechanical strength and heat resistance.
- the glass transition temperature of the component (A) may be adjusted by a combination of monomers.
- the glass transition temperature of the component (A) can be calculated from glass transition temperatures (Tg) (absolute temperature: K) of homopolymers of the monomers and mass fractions thereof based on the Fox equation shown below.
- Tg glass transition temperatures
- K absolute temperature
- 1 / Tg W 1 / Tg 1 + W 2 / Tg 2 + W 3 / Tg 3 + . + W n / Tg n
- Tg indicates the glass transition temperature (K) of the polymer to be calculated
- W 1 to W n each indicate a mass fraction of each monomer
- Tg 1 to Tg n each indicate the glass transition temperature (K) of a homopolymer of each monomer.
- the glass transition temperature is 165 °C in the case of a homopolymer of acrylamide, is 106 °C in the case of a homopolymer of acrylic acid, is -15 °C in the case of a homopolymer of hydroxyethyl acrylate, and is 105 °C in the case of a homopolymer of acrylonitrile.
- the monomer composition constituting the component (A) can be determined.
- the glass transition temperature of a homopolymer of a monomer can be measured by a differential scanning calorimeter (DSC), a differential thermal analyzer (DTA), a thermomechanical measurement apparatus (TMA) or the like under the condition that the temperature is raised from -100 °C to 300 °C (at a temperature rising rate of 10 °C/min).
- DSC differential scanning calorimeter
- DTA differential thermal analyzer
- TMA thermomechanical measurement apparatus
- a weight average molecular weight (Mw) of the component (A) is not particularly limited, and its upper limit and lower limit are, for example, 7,000,000, 6,500,000, 6,000,000, 5,500,000, 5,000,000, 4,500,000, 4,000,000, 3,500,000, 3,000,000, 2,500,000, 2,000,000, 1,500,000, 1,000,000, 950,000, 900,000, 850,000, 800,000, 750,000, 700,000, 650,000, 600,000, 550,000, 500,000, 450,000, 400,000, 350,000, 300,000, 250,000, 200,000, 150,000, and 100,000.
- 100,000 to 7,000,000 are preferable, and 350,000 to 6,000,000 are more preferable.
- a number average molecular weight (Mn) of the component (A) is not particularly limited, and its upper limit and lower limit are, for example, 6,000,000, 5,500,000, 5,000,000, 4,500,000, 4,000,000, 3,500,000, 3,000,000, 2,500,000, 2,000,000, 1,500,000, 1,000,000, 950,000, 900,000, 850,000, 800,000, 750,000, 700,000, 650,000, 600,000, 550,000, 500,000, 450,000, 400,000, 300,000, 200,000, 100,000, 50,000, and 10,000.
- the number average molecular weight (Mn) of the component (A) is preferably 10,000 or more.
- the weight average molecular weight and the number average molecular weight may be calculated, for example, as values in terms of polyacrylic acid as measured by gel permeation chromatography (GPC) in an appropriate solvent.
- GPC gel permeation chromatography
- the upper limit and lower limit of a molecular weight distribution (Mw/Mn) of the component (A) are, for example, 15, 14, 13, 11, 10, 9, 7.5, 5, 4, 3, 2.9, 2.5, 2, 1.5, and 1.1.
- the molecular weight distribution (Mw/Mn) of the component (A) is preferably 1.1 to 15.
- B-type viscosity of an aqueous solution containing 13% by mass of the component (A) is not particularly limited, and its upper limit and lower limit are, for example, 100,000 mPa ⁇ s, 90,000 mPa ⁇ s, 80,000 mPa ⁇ s, 70,000 mPa ⁇ s, 60,000 mPa ⁇ s, 50,000 mPa ⁇ s, 45,000 mPa ⁇ s, 40,000 mPa ⁇ s, 30,000 mPa ⁇ s, 20,000 mPa ⁇ s, 10,000 mPa ⁇ s, 9,000 mPa ⁇ s, 8,000 mPa ⁇ s, 7,000 mPa ⁇ s, 6,000 mPa ⁇ s, 5,000 mPa ⁇ s, 5,000 mPa ⁇ s, 4,000 mPa ⁇ s, 3,000 mPa ⁇ s, 2,000 mPa ⁇ s, 1,000 mPa ⁇ s, 900 mPa ⁇ s, 700 mPa ⁇ s, 500 mPa ⁇ s
- the B-type viscosity is measured by a B-type viscometer such as "B-type Viscometer Model BM” (product name) made by Toki Sangyo Co., Ltd.
- the upper limit and lower limit of the pH of the binder aqueous solution for a lithium-ion battery are, for example, 9, 8.9, 8.5, 8, 7.9, 7.5, 7, 6.9, 6.5, 6, 5.9, 5.6, 5.5, 5.4, 5.2, 5.1, 5, and 4.
- the pH of the binder aqueous solution for a lithium-ion battery is preferably 4 to 9 and more preferably 4 to 7 from the viewpoint of solution stability.
- the pH may be measured at 25 °C using a glass electrode pH meter (for example, "Handy pH Meter D-52" (product name) made by Horiba, Ltd.).
- a glass electrode pH meter for example, "Handy pH Meter D-52" (product name) made by Horiba, Ltd.
- the upper limit and lower limit of the content of the component (A) with respect to 100% by mass of the binder aqueous solution for a lithium-ion battery are, for example, 20% by mass, 19% by mass, 15% by mass, 14% by mass, 12% by mass, 10% by mass, 9% by mass, 7% by mass, 6% by mass, and 5% by mass.
- the content of the component (A) with respect to 100% by mass of the binder aqueous solution for a lithium-ion battery is preferably 5% by mass to 20% by mass.
- the upper limit and lower limit of the content of water with respect to 100% by mass of the binder aqueous solution for a lithium-ion battery are, for example, 95% by mass, 90% by mass, 85% by mass, and 80% by mass.
- the content of the water with respect to 100% by mass of the binder aqueous solution for a lithium-ion battery is preferably 80% by mass to 95% by mass.
- the upper limit and lower limit of a mass ratio between the component (A) and the water contained in the binder aqueous solution for a lithium-ion battery are, for example, 0.25, 0.2, 0.15, 0.1, and 0.05. In one embodiment, the mass ratio between the component (A) and the water contained in the binder aqueous solution for a lithium-ion battery is preferably 0.05 to 0.25.
- the above binder aqueous solution for a lithium-ion battery contains a dispersion (emulsion).
- dispersion examples include styrene-butadiene-based copolymer latex, polystyrene-based polymer latex, polybutadiene-based polymer latex, acrylonitrile-butadiene-based copolymer latex, polyurethane-based polymer latex, polymethylmethacrylate-based polymer latex, methylmethacrylate-butadiene-based copolymer latex, polyacrylate-based polymer latex, vinyl chloride-based polymer latex, vinyl acetate-based polymer emulsion, vinyl acetate-ethylene-based copolymer emulsion, polyethylene emulsion, carboxy-modified styrene-butadiene copolymer resin emulsion, acrylic resin emulsion, polyethylene, polypropylene, polyethylene terephthalate, polyamide (PA), polyimide (PI), polyamide-imide (PAI), an aromatic polyamide, alginic
- the upper limit and lower limit of the content of the dispersion (emulsion) with respect to 100% by mass of the component (A) are, for example, 50% by mass, 45% by mass, 40% by mass, 35% by mass, 30% by mass, 25% by mass, 20% by mass, 19% by mass, 17% by mass, 15% by mass, 13% by mass, 10% by mass, 9% by mass, 7% by mass, 5% by mass, 4% by mass, 2% by mass, 1% by mass, and 0% by mass.
- the amount of the dispersion (emulsion) added with respect to 100% by mass of the component (A) is preferably 0% by mass to 50% by mass.
- the binder aqueous solution for a lithium-ion battery may contain, as an additive, a component that does not correspond to any of the component (A), water, and the dispersion (emulsion).
- Examples of the additive include a dispersant, a leveling agent, an antioxidant, and a thickener.
- the content of the additive is, for example, 0% by mass to 5% by mass, less than 1% by mass, less than 0.1% by mass, less than 0.01% by mass, or 0% by mass, with respect to 100% by mass of the component (A).
- the content of the additive is preferably 5% by mass or less with respect to 100% by mass of the component (A) from the viewpoint that haze is generated in the binder when the content exceeds 5% by mass.
- the content of the additive is, for example, 0% by mass to 5% by mass, less than 1% by mass, less than 0.1% by mass, less than 0.01% by mass, or 0% by mass, with respect to 100% by mass of the above aqueous solution.
- dispersant examples include an anionic dispersant, a cationic dispersant, a nonionic dispersant, and a polymer dispersant.
- the leveling agent examples include a surfactant, such as an alkyl-based surfactant, a silicon-based surfactant, a fluorine-based surfactant, and a metal-based surfactant.
- a surfactant such as an alkyl-based surfactant, a silicon-based surfactant, a fluorine-based surfactant, and a metal-based surfactant.
- antioxidants examples include a phenol compound, a hydroquinone compound, an organophosphorus compound, a sulfur compound, a phenylenediamine compound, and a polymer type phenol compound.
- the polymer type phenol compound is a polymer having a phenol structure in a molecule.
- a weight average molecular weight of the polymer type phenol compound is preferably 200 to 1,000, more preferably 600 to 700.
- the thickener examples include: a cellulosic polymer, such as carboxymethyl cellulose, methyl cellulose, and hydroxypropyl cellulose, as well as an ammonium salt and an alkali metal salt thereof; (modified) poly(meth)acrylic acid as well as an ammonium salt and an alkali metal salt thereof; polyvinyl alcohols, such as (modified) polyvinyl alcohol, a copolymer of acrylic acid or acrylate and vinyl alcohol, a copolymer of maleic anhydride, maleic acid, or fumaric acid and vinyl alcohol; polyethylene glycol, polyethylene oxide, polyvinylpyrrolidone, modified polyacrylic acid, oxidized starch, phosphoric acid starch, casein, various modified starches, and an acrylonitrile-butadiene copolymer hydride.
- a cellulosic polymer such as carboxymethyl cellulose, methyl cellulose, and hydroxypropyl cellulose, as well as an ammonium salt
- the binder aqueous solution for a lithium-ion battery may be used as a binder aqueous solution for a lithium-ion battery electrode, or a binder aqueous solution for a lithium-ion battery negative electrode.
- the disclosure provides a slurry for a lithium-ion battery negative electrode, the slurry containing the above binder aqueous solution for a lithium-ion battery and a negative electrode active material (B).
- slurry means a suspension of liquid and solid particles.
- the upper limit and lower limit of the content of the component (A) with respect to 100% by mass of the above slurry are, for example, 99.9% by mass, 95% by mass, 90% by mass, 80% by mass, 70% by mass, 60% by mass, 50% by mass, 40% by mass, 30% by mass, 20% by mass, 10% by mass, 5% by mass, 1% by mass, 0.5% by mass, 0.2% by mass, and 0.1% by mass.
- the content of the component (A) is preferably 0.1% by mass to 99.9% by mass with respect to 100% by mass of the above slurry.
- Examples of the water include ultrapure water, pure water, distilled water, ion-exchanged water, and tap water.
- the upper limit and lower limit of the content of the water with respect to 100% by mass of the above slurry are, for example, 70% by mass, 65% by mass, 60% by mass, 55% by mass, 50% by mass, 45% by mass, 40% by mass, 35% by mass, and 30% by mass.
- the content of the water is preferably 30% by mass to 70% by mass with respect to 100% by mass of the above slurry.
- a negative electrode active material may be used singly or in combination of two or more.
- the negative electrode active material is not particularly limited as long as being capable of reversibly occluding and releasing lithium, and an appropriate material may be suitably selected depending on the type of the target lithium-ion battery.
- the negative electrode active material may be used singly or in combination of two or more.
- Examples of the negative electrode active material include a carbon material, as well as a material alloyable with lithium, such as a silicon material, a lithium atom-containing oxide, a lead compound, a tin compound, an arsenic compound, an antimony compound, and an aluminum compound.
- Examples of the above carbon material include graphite (for example, natural graphite and artificial graphite) which is highly crystalline carbon, low crystalline carbon (such as soft carbon and hard carbon), carbon black (such as Ketjen black, acetylene black, channel black, lamp black, oil furnace black, and thermal black), a fullerene, a carbon nanotube, a carbon nanofiber, a carbon nanohorn, a carbon fibril, mesocarbon microbeads (MCMB), and a pitch-based carbon fiber.
- graphite for example, natural graphite and artificial graphite
- low crystalline carbon such as soft carbon and hard carbon
- carbon black such as Ketjen black, acetylene black, channel black, lamp black, oil furnace black, and thermal black
- MCMB mesocarbon microbeads
- silicon material examples include, in addition to silicon, silicon oxide and silicon alloy, silicon oxide composites expressed by SiC, SiO x C y (in which 0 ⁇ x ⁇ 3, and 0 ⁇ y ⁇ 5), Si 3 N 4 , Si 2 N 2 O, and SiO x (in which 0 ⁇ x ⁇ 2) (for example, materials described in Japanese Patent Laid-Open Nos. 2004-185810 and 2005-259697 ), and a silicon material described in Japanese Patent Laid-Open No. 2004-185810 .
- silicon materials described in Japanese Patent Nos. 5390336 and 5903761 may also be used.
- the above silicon oxide is preferably a silicon oxide expressed by a composition formula SiO x (in which 0 ⁇ x ⁇ 2, preferably 0.1 ⁇ x ⁇ 1).
- the above silicon alloy is preferably an alloy of silicon and at least one transition metal selected from the group consisting of titanium, zirconium, nickel, copper, iron and molybdenum. Silicon alloys of these transition metals are preferable due to high electronic conductivity and high strength.
- the silicon alloy is more preferably a silicon-nickel alloy or a silicon-titanium alloy, particularly preferably a silicon-titanium alloy.
- a content ratio of silicon in the silicon alloy is preferably 10 mol% or more, more preferably 20 mol% to 70 mol%, with respect to 100 mol% of metal elements in the above silicon alloy.
- the silicon material may be single crystalline, polycrystalline, or amorphous.
- a negative electrode active material other than the silicon material may be used together.
- a negative electrode active material include the above carbon material; a conductive polymer such as polyacene; a composite metal oxide expressed by A X B Y O Z (in which A represents an alkali metal or a transition metal, B represents at least one selected from transition metals such as cobalt, nickel, aluminum, tin, and manganese, O represents an oxygen atom, and X, Y, and Z are respectively numbers in the following ranges: 0.05 ⁇ X ⁇ 1.10, 0.85 ⁇ Y ⁇ 4.00 and 1.5 ⁇ Z ⁇ 5.00), or other metal oxide.
- the silicon material is used as the negative electrode active material, it is preferable to use a carbon material together because a volume change associated with the occlusion and release of lithium is small.
- lithium-containing oxide examples include a ternary nickel cobalt lithium manganate, a lithium-transition metal composite oxide, such as a lithium-manganese composite oxide (such as LiMn 2 O 4 ), a lithium-nickel composite oxide (such as LiNiO 2 ), a lithium-cobalt composite oxide (such as LiCoO 2 ), a lithium-iron composite oxide (such as LiFeO 2 ), a lithium-nickel-manganese composite oxide (such as LiNi 0.5 Mn 0.5 O 2 ), a lithium-nickel-cobalt composite oxide (such as LiNi 0.8 Co 0.2 O 2 ), a lithium-transition metal phosphate compound (such as LiFePO 4 ), a lithium-transition metal sulfate compound (such as Li x Fe 2 (SO 4 ) 3 ), a lithium-titanium composite oxide (such as lithium titanate: Li 4 Ti 5 O 12 ), and other conventionally known negative electrode active materials.
- the carbon material and/or the material alloyable with lithium is preferably contained in the negative electrode active material in an amount of 50% by mass or more, more preferably 80% by mass or more, further preferably 90% by mass or more, and particularly preferably 100% by mass.
- the negative electrode active material (B) is preferably a negative electrode active material containing 1% by mass or more (for example, 2% by mass or more, 5% by mass or more, 10% by mass or more, 25% by mass or more, 50% by mass or more, 75% by mass or more, 90% by mass or more, or 100% by mass) of silicon and/or a silicon oxide covered with a carbon layer.
- the shape of the negative electrode active material is not particularly limited and may be an arbitrary shape such as a fine particle shape or a thin film shape, and a fine particle shape is preferable.
- An average particle diameter of the negative electrode active material is not particularly limited, and its upper limit and lower limit are, for example, 50 ⁇ m, 45 ⁇ m, 40 ⁇ m, 35 ⁇ m, 30 ⁇ m, 25 ⁇ m, 20 ⁇ m, 15 ⁇ m, 10 ⁇ m, 5 ⁇ m, 4 ⁇ m, 3 ⁇ m, 2.9 ⁇ m, 2 ⁇ m, 1 ⁇ m, 0.5 ⁇ m, and 0.1 ⁇ m.
- the average particle diameter of the negative electrode active material is preferably 0.1 ⁇ m to 50 ⁇ m, more preferably 0.1 ⁇ m to 45 ⁇ m, further preferably 1 ⁇ m to 10 ⁇ m, and particularly preferably 5 ⁇ m.
- particle diameter means a maximum distance among distances between arbitrary two points on a contour line of a particle (the same applies hereinafter).
- average particle diameter means a value calculated as an average value of particle diameters of particles observed in several to several tens of visual fields using an observation means such as a scanning electron microscope (SEM) or a transmission electron microscope (TEM) (the same applies hereinafter).
- the upper limit and lower limit of the content of the component (A) in the above slurry with respect to 100% by mass of the negative electrode active material (B) are, for example, 15% by mass, 14% by mass, 13% by mass, 12% by mass, 11% by mass, 10% by mass, 9% by mass, 8% by mass, 7% by mass, 6% by mass, 5% by mass, 4% by mass, 3% by mass, 2% by mass, 1.5% by mass, 1% by mass, and 0.5 mass%.
- the above content is preferably 0.5% by mass to 15% by mass.
- a conductive aid may be contained in the above slurry.
- the conductive aid include fibrous carbon such as vapor grown carbon fiber (VGCF), a carbon nanotube (CNT) and carbon nanofiber (CNF), carbon black such as graphite particles, acetylene black, Ketjen black and furnace black, and fine powders of Cu, Ni, Al, Si or alloys thereof having an average particle diameter of 10 ⁇ m or less.
- the content of the conductive aid is not particularly limited, and is preferably 0% by mass to 10% by mass, more preferably 0.5% by mass to 6% by mass, with respect to the negative electrode active material component.
- a slurry viscosity adjustment solvent is not particularly limited, and may include a non-aqueous medium having a normal boiling point of 80 °C to 350 °C.
- the slurry viscosity adjustment solvent may be used singly or in combination of two or more.
- the slurry viscosity adjustment solvent examples include: an amide solvent, such as N-methylpyrrolidone, dimethylformamide, and N,N-dimethylacetamide; a hydrocarbon solvent, such as toluene, xylene, n-dodecane, and tetralin; an alcohol solvent, such as methanol, ethanol, 2-propanol, isopropyl alcohol, 2-ethyl-1-hexanol, 1-nonanol, and lauryl alcohol; a ketone solvent, such as acetone, methyl ethyl ketone, cyclohexanone, phorone, acetophenone, and isophorone; an ether solvent, such as dioxane and tetrahydrofuran (THF); an ester solvent, such as benzyl acetate, isopentyl butyrate, methyl lactate, ethyl lactate, and butyl lactate; an amine solvent
- N-methylpyrrolidone is preferable from the viewpoint of application workability.
- the content of the above non-aqueous medium is not particularly limited, and is preferably 0% by mass to 10% by mass with respect to 100% by mass of the above slurry.
- the above slurry may contain, as an additive, a component that does not correspond to any of the component (A), the component (B), water, the conductive aid, and the slurry viscosity adjustment solvent without impairing the effects of the disclosure.
- a component that does not correspond to any of the component (A), the component (B), water, the conductive aid, and the slurry viscosity adjustment solvent without impairing the effects of the disclosure.
- the additive include those described above.
- the content of the additive is, for example, 0% by mass to 5% by mass, less than 1% by mass, less than 0.1% by mass, less than 0.01% by mass, or 0% by mass, with respect to 100% by mass of the component (A).
- the content of the additive with respect to 100% by mass of the component (B) is, for example, 0% by mass to 5% by mass, less than 1% by mass, less than 0.1% by mass, less than 0.01% by mass, or 0% by mass.
- the dispersion (emulsion) may be contained in a larger amount than the above additive content.
- the upper limit and lower limit of the content of the dispersion (emulsion) with respect to 100% by mass of the slurry for a lithium-ion battery negative electrode are, for example, 20% by mass, 19% by mass, 17% by mass, 15% by mass, 13% by mass, 10% by mass, 9% by mass, 7% by mass, 5% by mass, 4% by mass, 2% by mass, 1% by mass, and 0% by mass.
- the amount of the dispersion (emulsion) added with respect to 100% by mass of the above aqueous solution or the slurry for a lithium-ion battery negative electrode is preferably less than 5% by mass.
- the above slurry is prepared by mixing the component (A), the component (B), water, and if necessary, the conductive aid and the slurry viscosity adjustment solvent.
- Examples of a means of mixing the slurry include a ball mill, a sand mill, a pigment disperser, a Raikai mixer, an ultrasonic disperser, a homogenizer, a planetary mixer, and a Hobart mixer.
- the disclosure provides a negative electrode for a lithium-ion battery, obtained by applying the above slurry for a lithium-ion battery negative electrode to a current collector, and drying and curing the slurry.
- the above lithium-ion battery negative electrode has a cured product of the above slurry for a lithium-ion battery negative electrode on a surface of the current collector.
- a material of the current collector is not particularly limited, and examples thereof include a metal material, such as copper, iron, aluminum, nickel, stainless steel, and nickel-plated steel, or a carbon material, such as carbon cloth and carbon paper.
- the form of the current collector is not particularly limited.
- examples thereof include a metal foil, a metal cylinder, a metal coil, and a metal plate;
- examples thereof include a carbon plate, a carbon thin film, and a carbon cylinder.
- a copper foil is preferably used as the current collector because it is currently used in industrialized products.
- the application means is not particularly limited, and examples thereof include a conventionally known coating device, such as a comma coater, a gravure coater, a micro gravure coater, a die coater, and a bar coater.
- a conventionally known coating device such as a comma coater, a gravure coater, a micro gravure coater, a die coater, and a bar coater.
- the drying means is also not particularly limited, and the temperature is preferably 60 °C to 200 °C, more preferably 100 °C to 195 °C.
- the atmosphere may be dry air or an inert atmosphere.
- the thickness of the negative electrode (cured product) is not particularly limited, and is preferably 5 ⁇ m to 300 ⁇ m, more preferably 10 ⁇ m to 250 ⁇ m. By setting the above range, a function of occluding and releasing sufficient lithium with respect to a high-density current value may be easily obtained.
- the disclosure provides a lithium-ion battery including the above negative electrode for a lithium-ion battery.
- the above battery includes an electrolyte solution, a separator, a positive electrode and so on. The above are not particularly limited.
- electrolyte solution examples include non-aqueous electrolytic solution in which a supporting electrolyte is dissolved in a non-aqueous solvent.
- a film forming agent may be contained in the above non-aqueous electrolytic solution.
- non-aqueous solvent various known ones may be used without particular limitation, and may be used singly or in combination of two or more.
- examples of the non-aqueous solvent include: a chain carbonate solvent, such as diethyl carbonate, dimethyl carbonate, and ethyl methyl carbonate; a cyclic carbonate solvent, such as ethylene carbonate, propylene carbonate, and butylene carbonate; a chain ether solvent, such as 1,2-dimethoxyethane; a cyclic ether solvent, such as tetrahydrofuran, 2-methyltetrahydrofuran, sulfolane, and 1,3-dioxolane; a chain ester solvent, such as methyl formate, methyl acetate, and methyl propionate; a cyclic ester solvent, such as ⁇ -butyrolactone and ⁇ -valerolactone; and acetonitrile.
- a combination of mixed solvents containing a cyclic carbonate such
- a lithium salt is used as the supporting electrolyte.
- the lithium salt various known ones may be used without particular limitation, and may be used singly or in combination of two or more.
- the supporting electrolyte include LiPF6, LiAsF6, LiBF4, LiSbF6, LiAlCl 4 , LiClO 4 , CF 3 SO 3 Li, C 4 F 9 SO 3 Li, CF 3 COOLi, (CF 3 CO) 2 NLi, (CF 3 SO 2 ) 2 NLi, and (C 2 F 5 SO 2 )NLi.
- LiPF 6 , LiClO 4 and CF 3 SO 3 Li which are easily dissolved in a solvent and exhibit a high dissociation degree, are preferable.
- the higher the dissociation degree of the supporting electrolyte the higher the lithium-ion conductivity. Therefore, the lithium-ion conductivity can be adjusted according to the type of the supporting electrolyte.
- the film forming agent various known ones may be used without particular limitation, and may be used singly or in combination of two or more.
- the film forming agent include: a carbonate compound, such as vinylene carbonate, vinyl ethylene carbonate, vinyl ethyl carbonate, methylphenyl carbonate, fluoroethylene carbonate, and difluoroethylene carbonate; an alkene sulfide, such as ethylene sulfide and propylene sulfide; a sultone compound, such as 1,3-propane sultone and 1,4-butane sultone; and an acid anhydride, such as maleic anhydride and succinic anhydride.
- a carbonate compound such as vinylene carbonate, vinyl ethylene carbonate, vinyl ethyl carbonate, methylphenyl carbonate, fluoroethylene carbonate, and difluoroethylene carbonate
- an alkene sulfide such as ethylene sulfide and propylene sul
- the content of the film forming agent in the electrolyte solution is not particularly limited, and is 10% by mass or less, 8% by mass or less, 5% by mass or less, or 2% by mass or less, in order of preference.
- the advantages of the film forming agent such as suppression of initial irreversible capacity or improvement in low temperature characteristics and rate characteristics, may be easily achieved.
- the separator is an article interposed between a positive electrode and a negative electrode, and is used to prevent a short circuit between the electrodes.
- a porous separator such as a porous film or a nonwoven fabric may be preferably used, which is impregnated with the aforementioned non-aqueous electrolytic solution for use.
- a polyolefin such as polyethylene and polypropylene, or polyethersulfone, is used, and polyolefin is preferable.
- the positive electrode various known ones may be used without particular limitation.
- the positive electrode include one obtained by preparing a slurry by mixing a positive electrode active material, a conductive aid, and a binder for a positive electrode with an organic solvent, applying the prepared slurry to a positive electrode current collector and drying and pressing.
- Examples of the positive electrode active material include an inorganic positive electrode active material and an organic positive electrode active material.
- Examples of the inorganic positive electrode active material include a transition metal oxide, a composite oxide of lithium and a transition metal, and a transition metal sulfide. Examples of the above transition metal include Fe, Co, Ni, Mn, and Al.
- Examples of the inorganic compound used in the positive electrode active material include: a lithium-containing composite metal oxide, such as LiCoO 2 , LiNiO 2 , LiMnO 2 , LiMn 2 O 4 , LiFePO 4 , LiNi 1/2 Mn 3/2 O 4 , LiCo 1/3 Ni 1/3 Mn 1/3 O 2 , Li[Li 0.1 Al 0.1 Mn 1.8 ]O 4 , and LiFeVO 4 ; a transition metal sulfide, such as TiS 2 , TiS 3 , and amorphous MoS2; and a transition metal oxide, such as Cu 2 V 2 O 3 , amorphous V 2 O-P 2 O 5 , MoO 3 , V 2 O 5 , and V 6 O 13 .
- a lithium-containing composite metal oxide such as LiCoO 2 , LiNiO 2 , LiMnO 2 , LiMn 2 O 4 , LiFePO 4 , LiNi 1/2 Mn 3/2 O 4 , LiCo
- organic positive electrode active material examples include a conductive polymer, such as polyacetylene and poly-p-phenylene.
- An iron-based oxide having poor electric conductivity may be used as an electrode active material covered with a carbon material by allowing a carbon source material to exist during reduction firing. These compounds may be partially element-substituted.
- LiCoO 2 , LiNiO 2 , LiMnO 2 , LiMn 2 O 4 , LiFePO4, LiNi 1/2 Mn 3/2 O 4 , LiCo 1/3 Ni 1/3 Mn 1/3 O 2 , and Li[Li 0.1 Al 0.1 Mn 1.8 ]O 4 are preferable.
- the conductive aid examples include fibrous carbon such as vapor grown carbon fiber (VGCF), a carbon nanotube (CNT) and carbon nanofiber (CNF), carbon black such as graphite particles, acetylene black, Ketjen black and furnace black, and fine powders of Cu, Ni, Al, Si or alloys thereof having an average particle diameter of 10 ⁇ m or less.
- fibrous carbon such as vapor grown carbon fiber (VGCF), a carbon nanotube (CNT) and carbon nanofiber (CNF), carbon black such as graphite particles, acetylene black, Ketjen black and furnace black, and fine powders of Cu, Ni, Al, Si or alloys thereof having an average particle diameter of 10 ⁇ m or less.
- the binder for a positive electrode various known ones may be used without particular limitation, and may be used singly or in combination of two or more thereof.
- the binder for a positive electrode include a fluorine-based resin (such as polyvinylidene fluoride and polytetrafluoroethylene), a polyolefin (such as polyethylene and polypropylene), a polymer having an unsaturated bond (such as styrene-butadiene rubber, isoprene rubber, and butadiene rubber), and an acrylic acid-based polymer (such as an acrylic acid copolymer and a methacrylic acid copolymer).
- a fluorine-based resin such as polyvinylidene fluoride and polytetrafluoroethylene
- a polyolefin such as polyethylene and polypropylene
- a polymer having an unsaturated bond such as styrene-butadiene rubber, isoprene rubber, and butadiene rubber
- Examples of the positive electrode current collector include an aluminum foil and a stainless steel foil.
- the form of the above lithium-ion battery is not particularly limited.
- Examples of the form of the lithium-ion battery include a cylinder type in which a sheet electrode and a separator are formed in a spiral shape, a cylinder type having an inside-out structure in which a pellet electrode and a separator are combined, and a coin type in which a pellet electrode and a separator are laminated.
- the battery can be used in an arbitrary shape such as a coin shape, a cylindrical shape, and a square shape.
- a method for producing the above lithium-ion battery is not particularly limited, and the lithium-ion battery may be assembled by an appropriate procedure depending on the structure of the battery.
- Examples of the method for producing a lithium-ion battery include a method described in Japanese Patent Laid-Open No. 2013-089437 .
- the battery can be produced in the following manner. A negative electrode is placed on an exterior case, an electrolytic solution and a separator are provided thereon, a positive electrode is further placed so as to face the negative electrode, and the positive electrode is fixed with a gasket and a sealing plate.
- a binder aqueous solution containing a water-soluble poly(meth)acrylamide was prepared in the same manner as in Preparation Example 5 except that the monomer composition and the amount of the neutralizer were changed to those shown in the following table.
- Comparative Preparation Example 1 a binder aqueous solution containing a water-soluble poly(meth)acrylamide was prepared in the same manner as in Comparative Preparation Example 1 except that the monomer composition and the like in Comparative Preparation Example 1 were changed to those shown in the following table.
- No. 3 rotor was used at a rotational speed of 6 rpm.
- the weight average molecular weight was calculated as a value in terms of polyacrylic acid as measured by gel permeation chromatography (GPC) under a 0.2 M phosphate buffer/acetonitrile solution (90/10, PH 8.0).
- GPC gel permeation chromatography
- SB-806M-HQ made by SHODEX was used as a column.
- a slurry was prepared using a commercially available homodisper ("Homodisper Model 2.5" made by PRIMIX Corporation).
- the binder aqueous solution for a lithium-ion battery as obtained in Preparation Example 1 which contained the water-soluble poly(meth)acrylamide (A), was mixed in an amount of 5 parts by mass in terms of solid content with 20 parts by mass of silicon monoxide particles ("CC Powder” made by OSAKA Titanium technologies Co., Ltd.) having a D50 (median diameter) of 5 ⁇ m, 80 parts by mass of artificial graphite (“G1-A#” made by Jiangxi Zichen Technology Co., Ltd.) having a D50 (median diameter) of 20 ⁇ m, and 1 part by mass of a conductive aid ("Super C65” made by Imerys Graphite & Carbon Japan K.K.).
- Ion-exchanged water was added thereto so as to achieve a solid content concentration of 47%, and the container was set in the above homodisper. Next, the resultant was kneaded at 3,000 rpm for 10 minutes. After that, the resultant was subjected to defoaming for 1 minute using a rotation/revolution mixer ("Awatori Rentaro" made by THINKY CORPORATION), and a slurry for an electrode was obtained.
- Example 1 a slurry was prepared in the same manner as in Example 1 except that the composition in Example 1 was changed to those shown in the following table.
- the storage stability of the electrode slurry was evaluated as follows.
- the electrode flexibility was evaluated as follows.
- the above slurry for a lithium-ion battery was uniformly applied to a surface of a current collector (20 ⁇ m) composed of copper foil by a doctor blade method so that a film thickness after drying would be 170 ⁇ m, then subjected to heating and drying at 150 °C for 15 minutes, and an electrode was obtained.
- the obtained electrode was cut into a width of 10 mm and a length of 70 mm, and was wound around a TeflonTM rod having a diameter of 30 mm0 with an active material layer facing outward. A state of a surface of the active material layer was observed and evaluated according to the following criteria.
- the electrode adhesion was evaluated as follows.
- the above slurry for a lithium-ion battery was uniformly applied to a surface of a current collector (20 ⁇ m) composed of copper foil by a doctor blade method so that a film thickness after drying would be 170 ⁇ m. After drying at 150 °C for 30 minutes, the resultant was subjected to a heating treatment at 150 °C in vacuum for 120 minutes. After that, by press processing with a roll press machine to achieve a film (electrode active material layer) density of 1.5 g/cm 3 , an electrode was obtained. A test piece of 2 cm in width ⁇ 10 cm in length was cut out from the obtained electrode and fixed with a coating surface facing up.
- an adhesive tape (“CELLOTAPETM” made by NICHIBAN Co., Ltd.) (specified in JIS Z1522) of 15 mm in width was attached while being pressed onto a surface of an active material layer of the test piece, and then the stress when the adhesive tape was peeled off from one end of the test piece at a speed of 30 mm/min in the 180 ° direction was measured using a tensile tester ("TENSILON RTM-100” made by A&D Company, Limited) at 25 °C. The measurement was performed twice, the measured stress was converted into a value per width of 15 mm, and an average value thereof was calculated as peel strength.
- the above slurry for a lithium-ion battery was uniformly applied to a surface of a current collector (20 ⁇ m) composed of copper foil by a doctor blade method so that a film thickness after drying would be 170 ⁇ m. After drying at 150 °C for 30 minutes, the resultant was subjected to a heating treatment at 150 °C in vacuum for 120 minutes. After that, by press processing with a roll press machine to achieve a film (electrode active material layer) density of 1.5 g/cm 3 , an electrode was obtained.
- the above electrode was punched and formed to have a diameter of 16 mm, and the resultant was placed inside a packing above an aluminum lower lid of a test cell (made by Nippon Tomcell Co., Ltd.).
- a separator ("Selion P2010" made by CS Tech Co., Ltd.) composed of a polypropylene porous film punched out to a diameter of 24 mm was placed.
- electrolytic solution was a solution in which LiPF 6 was dissolved at a concentration of 1 mol/L in a solvent having a mass ratio of ethylene carbonate to ethyl methyl carbonate of 1/1.
- the lithium half-cell was put in a constant temperature bath set to 25 °C and underwent charging and discharging as follows.
- the charging was started at a constant current (0.1 C) and was completed (cutoff) when the voltage reached 0.01 V.
- the discharging was started at a constant current (0.1 C) and was completed (cutoff) when the voltage reached 1.0 V.
- the above charging and discharging were repeated 30 times.
- “1 C” indicates a current value at which a cell having a certain electric capacity is discharged at a constant current and the discharging is completed in 1 hour.
- “0.1 C” means a current value at which it takes 10 hours to complete discharging
- “10 C” means a current value at which it takes 0.1 hour to complete discharging.
- Discharge capacity retention rate discharge capacity at 30 th cycle / discharge capacity at 1 st cycle ⁇ 100 %
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Dispersion Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
CH2=C(R1)-CO-O-R2-O-R3 (1)
(in which R1 is a hydrogen atom or a methyl group, R2 is an alkylene group having 1 to 4 carbon atoms, R3 is an alkyl group having 1 to 4 carbon atoms, and a total number of carbon atoms of the groups R1, R2 and R3 is 5 or less.)
Description
- The disclosure relates to a binder aqueous solution for a lithium-ion battery, a slurry for a lithium-ion battery negative electrode, a negative electrode for a lithium-ion battery, and a lithium-ion battery.
- Lithium-ion batteries have a small size, light weight and high energy density, and further, are repeatedly chargeable and dischargeable, and are used in a wide range of applications. Hence, in recent years, improvements to battery members such as electrodes have been studied with the aim of improving the performance of lithium-ion batteries.
- The positive electrode and negative electrode of a lithium-ion battery are both produced in the following manner. A slurry prepared by dispersing an electrode active material and a binder resin in a solvent is applied on both sides of a current collector (for example, a metal foil), and after the solvent is dried and removed to form an electrode layer, the resultant is compression-molded by a roll press machine or the like.
- In recent years, in an electrode for a lithium-ion battery, various electrode active materials have been proposed from the viewpoint of increasing battery capacity. However, depending on the electrode active material, the electrode for a lithium-ion battery is likely to expand and contract with charging and discharging. Hence, the electrode for a lithium-ion battery that is likely to expand and contract with charging and discharging undergoes a volume change (springback) from the initial stage of repetition of charging and discharging, and a lithium-ion battery using the above electrode is likely to deteriorate in electrical characteristics such as cycle characteristics.
- Therefore, in this field, studies have been made to solve the above problem by binder resins. For example, it has been proposed that good charge and discharge characteristics can be obtained by using polyacrylamide (Patent Documents 1 and 2) as a binder of a water-soluble resin. In addition, with respect to expansion and contraction of an active material associated with charging and discharging, it has been proposed to suppress the expansion by adding a crosslinker to a particulate resin being a binder resin (Patent Document 3). The crosslinker usually causes a crosslinking reaction in the drying step after the slurry composition is applied to the current collector, and forms crosslinks between particles of the particulate resin or the like.
-
- [Patent Document 1] Japanese Patent Laid-open No.
2015-118908 - [Patent Document 2] Japanese Patent Laid-open No.
2015-106488 - [Patent Document 3]
WO 2015/098507 - However, when crosslinking is performed using a crosslinker, flexibility of the binder resin is reduced, and as a result, a problem may occur in which adhesion to the electrode is reduced.
- Therefore, problems to be solved by the disclosure include to provide a binder aqueous solution for a lithium-ion battery, the binder aqueous solution imparting a good discharge capacity retention rate to a lithium-ion battery, good electrode flexibility and electrode adhesion to an electrode, and good storage stability to a slurry.
- As a result of intensive studies, the inventors have found that the above problems can be solved by a water-soluble polymer containing a predetermined unsaturated monomer as a component.
- According to the disclosure, the following items are provided.
- (Item 1) A binder aqueous solution for a lithium-ion battery, containing: a water-soluble poly(meth)acrylamide (A) being a polymer of a monomer group containing, with respect to 100 mol% of the monomer group, 30 mol% to 95 mol% of a (meth)acrylamide group-containing compound (a), and 5 mol% to 40 mol% of an alkoxyalkyl (meth)acrylate (b) represented by the following general formula (1),
CH2=C(R1)-CO-O-R2-O-R3 (1)
(in the formula, R1 is a hydrogen atom or a methyl group, R2 is an alkylene group having 1 to 4 carbon atoms, R3 is an alkyl group having 1 to 4 carbon atoms, and a total number of carbon atoms of the groups R1, R2 and R3 is 5 or less.) - (Item 2) A slurry for a lithium-ion battery negative electrode, containing the binder aqueous solution for a lithium-ion battery as described in the above Item and a negative electrode active material.
- (Item 3) A negative electrode for a lithium-ion battery, obtained by applying the slurry for a lithium-ion battery negative electrode as described in the above Item to a current collector, and drying and curing the slurry.
- (Item 4) A lithium-ion battery including the negative electrode for a lithium-ion battery as described in the above Item.
- In the disclosure, one or more of the features described above may be provided in combination in addition to the specified combinations.
- The binder aqueous solution for a lithium-ion battery according to the disclosure is capable of imparting excellent storage stability to a slurry for a lithium-ion battery negative electrode. In addition, the slurry for a lithium-ion battery negative electrode according to the disclosure has excellent storage stability. Further, the electrode according to the disclosure has excellent flexibility and adhesion. The battery according to the disclosure has an excellent discharge capacity retention rate.
- Throughout the disclosure, ranges of numerical values such as physical property values and content may be suitably set (for example, selected from the upper and lower limit values described in each item below). Specifically, regarding a numerical value α, when the upper limit and lower limit of the numerical value α are, for example, A4, A3, A2, and A1 (in which A4>A3>A2>A1), the numerical value α is in a range of, for example, A4 or less, A3 or less, A2 or less, A1 or more, A2 or more, A3 or more, A1 to A2, A1 to A3, A1 to A4, A2 to A3, A2 to A4, and A3 to A4.
- [Binder Aqueous Solution for Lithium-ion Battery: Also Referred to as Aqueous Solution]
The disclosure provides a binder aqueous solution for a lithium-ion battery, containing: a water-soluble poly(meth)acrylamide (A) being a polymer of a monomer group containing, with respect to 100 mol% of the monomer group, 30 mol% to 95 mol% of a (meth)acrylamide group-containing compound (a), and 5 mol% to 40 mol% of an alkoxyalkyl (meth)acrylate (b) represented by the following general formula (1),
CH2=C(R1)-CO-O-R2-O-R3 (1)
(in the formula, R1 is a hydrogen atom or a methyl group, R2 is an alkylene group having 1 to 4 carbon atoms, R3 is an alkyl group having 1 to 4 carbon atoms, and a total number of carbon atoms of the groups R1, R2 and R3 is 5 or less.) - In the disclosure, "water-soluble" means having an insoluble content of less than 0.5% by mass (less than 2.5 mg) when 0.5 g of a compound thereof is dissolved in 100 g of water at 25 °C.
- In the case where the component (A) is not water-soluble, since it does not dissolve in water, no aqueous solution is formed at all. As a result, the component (A) does not contribute to dispersion of the slurry. In addition, viscosity required for application of the slurry to a current collector cannot be imparted to the slurry.
- When 0.5 g of the component (A) is dissolved in 100 g of water, the insoluble content of the component (A) is, for example, less than 0.5% by mass, less than 0.4% by mass, less than 0.3% by mass, less than 0.2% by mass, less than 0.1% by mass, or 0% by mass.
- In the disclosure, "poly(meth)acrylamide" means a (co)polymer obtained by polymerizing a monomer group containing a (meth)acrylamide group-containing compound.
- In the disclosure, "(meth)acryl" means "at least one selected from the group consisting of acryl and methacryl." Similarly, "(meth)acrylate" means "at least one selected from the group consisting of acrylate and methacrylate." "(Meth)acryloyl" means "at least one selected from the group consisting of acryloyl and methacryloyl."
- In the disclosure, "(meth)acrylamide group-containing compound" means a compound having a (meth)acrylamide group. As the (meth)acrylamide group-containing compound, various known ones may be used without particular limitation, and may be used singly or in combination of two or more.
- In one embodiment, the (meth)acrylamide group-containing compound is expressed by the following structural formula:
- Examples of the alkyl group include linear alkyl group, branched alkyl group, and cycloalkyl group.
- The linear alkyl group is expressed by a general formula of -CnH2n+1 (in which n is an integer of 1 or more). Examples of the linear alkyl group include methyl group, ethyl group, propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, and n-decamethyl group.
- The branched alkyl group is a group in which at least one hydrogen of a linear alkyl group is substituted with an alkyl group. Examples of the branched alkyl group include i-propyl group, i-butyl group, s-butyl group, t-butyl group, diethylpentyl group, trimethylbutyl group, trimethylpentyl group, and trimethylhexyl group.
- Examples of the cycloalkyl group include monocyclic cycloalkyl group, crosslinked cyclic cycloalkyl group, and condensed cyclic cycloalkyl group.
- In the disclosure, "monocyclic" means having a cyclic structure formed by covalent bonding of carbons and without crosslinking structure therein. "Condensed cyclic" means having a cyclic structure in which two or more single rings share two atoms (that is, only one side of each ring is shared (condensed) with each other). "Crosslinked cyclic" means having a cyclic structure in which two or more single rings share three or more atoms.
- Examples of the monocyclic cycloalkyl group include cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclodecyl group, and 3,5,5-trimethylcyclohexyl group.
- Examples of the crosslinked cyclic cycloalkyl group include tricyclodecyl group, adamantyl group, and norbornyl group.
- Examples of the condensed cyclic cycloalkyl group include bicyclodecyl group.
- Examples of the above (meth)acrylamide group-containing compound (a) include (meth)acrylamide, N-isopropyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N,N-dimethylaminopropyl(meth)acrylamide, N-methylol(meth)acrylamide, diacetone(meth)acrylamide, maleic acid amide, (meth)acrylamide t-butylsulfonic acid, (meth)acryloylmorpholine, hydroxyethyl(meth)acrylamide, and a salt thereof. Examples of the above salt include dimethylaminopropyl(meth)acrylamide methyl chloride quaternary salt, and dimethylaminoethyl (meth)acrylate benzyl chloride quaternary salt. Among them, when (meth)acrylamide especially acrylamide is used, a binder can be prepared which has high water solubility, has a high interaction with an electrode active material, and improves slurry dispersibility or a binding property between electrode active materials inside an electrode.
- The upper limit and lower limit of the content of the (meth)acrylamide group-containing compound with respect to 100 mol% of the monomer group are, for example, 95 mol%, 90 mol%, 85 mol%, 80 mol%, 75 mol%, 70 mol%, 65 mol%, 60 mol%, 55 mol%, 50 mol%, 45 mol%, 40 mol%, 35 mol%, and 30 mol%. In one embodiment, the above content preferably ranges from 30 mol% to 95 mol%.
- The upper limit and lower limit of the content of the (meth)acrylamide group-containing compound with respect to 100% by mass of the monomer group are, for example, 95% by mass, 90% by mass, 85% by mass, 80% by mass, 75% by mass, 70% by mass, 65% by mass, 60% by mass, 55% by mass, 50% by mass, 45% by mass, 40% by mass, 35% by mass, 30% by mass, 25% by mass, and 20% by mass. In one embodiment, the content of the (meth)acrylamide group-containing compound with respect to 100% by mass of the monomer group is preferably 20% by mass to 95% by mass.
- A component (b) is a compound represented by the following general formula (1),
CH2=C(R1)-CO-O-R2-O-R3 (1)
(in the formula, R1 is a hydrogen atom or a methyl group, R2 is an alkylene group having 1 to 4 carbon atoms, R3 is an alkyl group having 1 to 4 carbon atoms, and a total number of carbon atoms of the groups R1, R2 and R3 is 5 or less.) As the above alkoxyalkyl (meth)acrylate, various known ones may be used without particular limitation, and may be used singly or in combination of two or more. - The upper limit and lower limit of the total number of carbon atoms of the groups R1, R2 and R3 are, for example, 5, 4, 3, and 2. In one embodiment, the total number of carbon atoms of the groups R1, R2 and R3 is defined as 5 or less from the viewpoints of ensuring the water solubility and the availability of the component (A). The reason is that, when the total number of carbon atoms exceeds 5, the water solubility of the alkoxyalkyl (meth)acrylate decreases and it is difficult to ensure the water solubility of the component (A). In addition, from the viewpoint of further improving storage stability of a negative electrode slurry, flexibility and adhesion of a negative electrode, and a discharge capacity retention rate of a lithium-ion battery, the above number of carbon atoms is more preferably 4 or less. From the same viewpoint, the number of carbon atoms of R3 is preferably 1.
- Since the total number of carbon atoms of the groups R1, R2 and R3 in general formula (1) is 5 or less, the storage stability of a negative electrode slurry, the flexibility and adhesion of a negative electrode, and the discharge capacity retention rate of a lithium-ion battery are improved. A reason thereof is as follows. The following is only one theory, and the disclosure is not intended to be bound thereby.
A monomer in which the total number of carbon atoms of the groups R1, R2 and R3 in general formula (1) exceeds 5 is a hydrophobic monomer. When the component (A) is produced using such a hydrophobic monomer, the water solubility of the component (A) decreases. Hence, surface tension of an aqueous solution containing the component (A) decreases. As a result, when a slurry is produced using the aqueous solution containing the component (A), bubbles are likely to be generated. If the bubbles are generated, the following problems may occur. - (1) When the slurry is produced, blades of a disperser collide with the bubbles, and dispersion of the slurry does not proceed. As a result, the storage stability deteriorates.
- (2) When the slurry containing the bubbles is applied to a current collector to produce an electrode, the electrode, after being dried and cured, may have holes caused by the bubbles. Cracking and peeling originate from the holes, and as a result, the electrode flexibility and the electrode adhesion decrease.
- Combinations of the groups R1, R2 and R3 are exemplified as follows.
[Table 1] -R1 -R2- -R3 Total number of carbon atoms of groups R1, R2 and R3 -H -CH2- -Me 2 -H -CH2- -CH2Me 3 -H -CH2- -CH2CH2Me 4 -H -CH2- -CH(Me)2 4 -H -CH2- -CH2CH2CH2Me 5 -H -CH2- -CH(Me)CH2CH3 5 -H -CH2- -CH2CH(Me)2 5 -H -CH2- -C(Me)3 5 -H -CH2CH2- -CH3 3 -H -CH(Me)- -CH3 3 -H -CH2CH2- -CH2Me 4 -H -CH(Me)- -CH2Me 4 -H -CH2CH2- -CH2CH2Me 5 -H -CH(Me)- -CH2CH2Me 5 -H -CH2CH2- -CH(Me)2 5 -H -CH(Me)- -CH(Me)2 5 -H -CH2CH2CH2- -Me 4 -H -CH2CH(Me)- -Me 4 -H -CH(Me)CH2- -Me 4 -H -C(Me)2- -Me 4 -H -CH2CH2CH2- -CH2Me 5 -H -CH2CH(Me)- -CH2Me 5 -H -CH(Me)CH2- -CH2Me 5 -H -C(Me)2- -CH2Me 5 -H -CH2CH2CH2CH2- -Me 5 -H -CH(Me)CH2CH2- -Me 5 -H -CH2CH(Me)CH2- -Me 5 -H -CH2CH2CH(Me)- -Me 5 -H -CH2C(Me)2- -Me 5 -H -C(Me)2CH2- -Me 5 -Me -CH2- -Me 3 -Me -CH2- -CH2Me 4 -Me -CH2- -CH2CH2Me 5 -Me -CH2- -CH(Me)2 5 -Me -CH2CH2- -Me 4 -Me -CH(Me)- -Me 4 -Me -CH2CH2- -CH2Me 5 -Me -CH(Me)- -CH2Me 5 -Me -CH2CH2CH2- -Me 5 -Me -CH2CH(Me)- -Me 5 -Me -CH(Me)CH2- -Me 5 -Me -C(Me)2- -Me 5
In R2, the left side is an ester bond side and the right side is an alkoxy group side. - Examples of the above alkoxyalkyl (meth)acrylate include methoxymethyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 1-methoxyethyl (meth)acrylate, 3-methoxypropyl (meth)acrylate, 2-methoxypropyl (meth)acrylate, 1-methoxypropyl (meth)acrylate, 4-methoxybutyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, 2-methoxybutyl (meth)acrylate, 1-methoxybutyl (meth)acrylate, ethoxymethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 1-ethoxyethyl (meth)acrylate, 3-ethoxypropyl (meth)acrylate, 2-ethoxypropyl (meth)acrylate, 1-ethoxypropyl (meth)acrylate, propoxymethyl (meth)acrylate, 2-propoxyethyl (meth)acrylate, 1-propoxyethyl (meth)acrylate, and butoxymethyl (meth)acrylate.
- The upper limit and lower limit of the content of the above alkoxyalkyl (meth)acrylate with respect to 100 mol% of the monomer group are, for example, 40 mol%, 35 mol%, 30 mol%, 25 mol%, 20 mol%, 15 mol%, 10 mol%, 9 mol%, and 5 mol%. In one embodiment, the above content preferably ranges from 5 mol% to 40 mol%.
- The upper limit and lower limit of the content of the above alkoxyalkyl (meth)acrylate with respect to 100% by mass of the monomer group are, for example, 60% by mass, 55% by mass, 50% by mass, 45% by mass, 40% by mass, 35% by mass, 30% by mass, 25% by mass, 20% by mass, 15% by mass, 10% by mass, and 5% by mass. In one embodiment, the content of the above alkoxyalkyl (meth)acrylate with respect to 100% by mass of the monomer group is preferably 5% by mass to 60% by mass.
- <Unsaturated Organic Acid or Salt Thereof (c): Also Referred to as Component (c)> In the disclosure, an unsaturated organic acid means a compound having an acidic group and a polymerizable unsaturated bond. The unsaturated organic acid may be used singly or in combination of two or more.
- A salt of an unsaturated organic acid means a salt of the above unsaturated organic acid. The salt of the unsaturated organic acid may be used singly or in combination of two or more.
- Examples of the unsaturated organic acid include unsaturated carboxylic acid, unsaturated sulfonic acid, and unsaturated phosphoric acid.
- Examples of the unsaturated carboxylic acid include (meth)acrylic acid, crotonic acid, maleic acid, fumaric acid, and itaconic acid.
- Examples of the unsaturated sulfonic acid include: α,β-ethylenically unsaturated sulfonic acid, such as vinylsulfonic acid, styrenesulfonic acid, and (meth)allylsulfonic acid; (meth)acrylamide t-butylsulfonic acid, 2-(meth)acrylamide-2-methylpropanesulfonic acid, 2-(meth)acrylamide-2-hydroxypropanesulfonic acid, 3-sulfopropane(meth)acrylic ester, and bis-(3-sulfopropyl)itaconic ester.
- Examples of the unsaturated phosphoric acid include vinylphosphonic acid, vinyl phosphate, bis((meth)acryloxyethyl) phosphate, diphenyl-2-(meth)acryloyloxyethyl phosphate, dibutyl-2-(meth)acryloyloxyethyl phosphate, dioctyl-2-(meth)acryloyloxyethyl phosphate, monomethyl-2-(meth)acryloyloxyethyl phosphate, and 3-(meth)acryloxy-2-hydroxypropanephosphoric acid.
- In the disclosure, a compound corresponding to both a (meth)acrylamide group-containing compound and an unsaturated organic acid is regarded as an unsaturated organic acid.
- Examples of a salt of an unsaturated organic acid include an inorganic salt of an unsaturated organic acid. An inorganic salt of an unsaturated organic acid refers to a salt whose cationic portion is a metal cation. Examples of an inorganic salt include alkali metal salt and alkaline earth metal salt.
- Examples of the alkali metal include lithium, sodium, and potassium.
- Examples of the alkaline earth metal include magnesium and calcium.
- The upper limit and lower limit of the content of the unsaturated organic acid or a salt thereof with respect to 100 mol% of the monomer group are, for example, 40 mol%, 35 mol%, 30 mol%, 25 mol%, 20 mol%, 15 mol%, 10 mol%, 5 mol%, and 0 mol%. In one embodiment, the above content is preferably 0 mol% to 40 mol %, and more preferably 10 mol% to 40 mol% from the viewpoint of improving the water solubility and slurry dispersibility of the component (A).
- The upper limit and lower limit of the content of the unsaturated organic acid or a salt thereof with respect to 100% by mass of the monomer group are, for example, 50% by mass, 45% by mass, 40% by mass, 35% by mass, 30% by mass, 25% by mass, 20% by mass, 15% by mass, 10% by mass, 5% by mass, and 0% by mass. In one embodiment, the content of the unsaturated organic acid or a salt thereof with respect to 100% by mass of the monomer group is preferably 0% by mass to 50% by mass.
- As a component (d), various known ones may be used without particular limitation, and may be used singly or in combination of two or more.
- In the disclosure, "hydroxyalkyl group having 2 to 4 carbon atoms" refers to a group in which one of hydrogen atoms constituting an alkyl group having 2 to 4 carbon atoms is substituted with a hydroxy group.
- Examples of the hydroxyalkyl(meth)acrylate having a hydroxyalkyl group having 2 to 4 carbon atoms include 1-hydroxyethyl(meth)acrylate, 2-hydroxyethyl(meth)acrylate, 1-hydroxypropyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate, 3-hydroxypropyl(meth)acrylate, 2-hydroxy-1-methylethyl(meth)acrylate, 1-hydroxy-2-methylethyl(meth)acrylate, 1-hydroxybutyl(meth)acrylate, 2-hydroxybutyl(meth)acrylate, 3-hydroxybutyl(meth)acrylate, 4-hydroxybutyl(meth)acrylate, 1-hydroxy-1-methyl-propyl(meth)acrylate, 2-hydroxy- 1-methyl-propyl(meth)acrylate, 3-hydroxy-1-methyl-propyl(meth)acrylate, 1-ethyl-2-hydroxyethyl(meth)acrylate, 1-hydroxy-2-methyl-propyl(meth)acrylate, 2-hydroxy-2-methyl-propyl(meth)acrylate, 3-hydroxy-2-methyl-propyl(meth)acrylate, and 1,1-dimethyl-2-hydroxyethyl(meth)acrylate.
- The upper limit and lower limit of the content of the hydroxyalkyl(meth)acrylate having a hydroxyalkyl group having 2 to 4 carbon atoms with respect to 100 mol% of the monomer group are, for example, 40 mol%, 35 mol%, 30 mol%, 25 mol%, 20 mol%, 15 mol%, 10 mol%, 5 mol%, and 0 mol%. In one embodiment, the above content is preferably 0 mol% to 40 mol %, and more preferably 5 mol% to 40 mol% from the viewpoint of improving the water solubility and electrode flexibility of the component (A).
- The upper limit and lower limit of the content of the hydroxyalkyl(meth)acrylate having a hydroxyalkyl group having 2 to 4 carbon atoms with respect to 100% by mass of the monomer group are, for example, 40% by mass, 35% by mass, 30% by mass, 25% by mass, 20% by mass, 15% by mass, 10% by mass, 5% by mass, and 0% by mass. In one embodiment, the content of the hydroxyalkyl(meth)acrylate (d) having hydroxyalkyl group having 2 to 4 carbon atoms with respect to 100% by mass of the monomer group is preferably 0% by mass to 40% by mass.
- An α,β-unsaturated nitrile may be used singly or in combination of two or more. The α,β-unsaturated nitrile can be suitably used for the purpose of imparting flexibility to an electrode. Examples of the α,β-unsaturated nitrile include (meth)acrylonitrile, α-chloro(meth)acrylonitrile, α-ethyl(meth)acrylonitrile, and vinylidene cyanide. Among them, (meth)acrylonitrile is preferable, and acrylonitrile is particularly preferable.
- The upper limit and lower limit of the content of the α,β-unsaturated nitrile with respect to 100 mol% of the monomer group are, for example, 40 mol%, 35 mol%, 30 mol%, 25 mol%, 20 mol%, 15 mol%, 10 mol%, 5 mol%, and 0 mol%. In one embodiment, the above content is preferably 0 mol% to 40 mol %, and more preferably 5 mol% to 40 mol% from the viewpoint of improving the electrode flexibility.
- The upper limit and lower limit of the content of the α,β-unsaturated nitrile with respect to 100 % by mass of the monomer group are exemplified by 30% by mass, 25% by mass, 20% by mass, 15% by mass, 10% by mass, 5% by mass, and 0% by mass. In one embodiment, the content of the α,β-unsaturated nitrile (e) with respect to 100% by mass of the monomer group is preferably 0% by mass to 30% by mass.
- The upper limit and lower limit of a molar ratio [amount of substance of component (b) / amount of substance of component (a)] between the component (b) and the component (a) contained in the monomer group are, for example, 1.3, 1, 0.9, 0.5, 0.2, 0.1, 0.09, and 0.05. In one embodiment, the above molar ratio is preferably 0.05 to 1.3.
- The upper limit and lower limit of a molar ratio [amount of substance of any one of the components (c) to (e) / amount of substance of component (a)] between any one of the components (c) to (e) and the component (a) contained in the monomer group are, for example, 1.3, 1, 0.9, 0.5, 0.2, 0.1, 0.09, 0.05 and 0. In one embodiment, the above molar ratio is preferably 0 to 1.3.
- The upper limit and lower limit of a molar ratio [amount of substance of any one of the components (c) to (e) / amount of substance of component (b)] between any one of the components (c) to (e) and the component (b) contained in the monomer group are, for example, 8, 7, 6, 5, 4, 3, 2, 1, 0.9, 0.5, 0.2, 0.1, 0.09, 0.05, and 0. In one embodiment, the above molar ratio is preferably 0 to 8.
- The upper limit and lower limit of a mass ratio [mass of component (b) / mass of component (a)] between the component (b) and the component (a) contained in the monomer group are, for example, 3, 2.5, 2, 1.5, 1, 0.9, 0.5, 0.2, 0.1, 0.09, and 0.05. In one embodiment, the above mass ratio is preferably 0.05 to 3.
- The upper limit and lower limit of a mass ratio [mass of component (c) / mass of component (a)] between the component (c) and the component (a) contained in the monomer group are, for example, 2.5, 2, 1.5, 1, 0.9, 0.5, 0.2, 0.1, 0.09, 0.05, and 0. In one embodiment, the above mass ratio is preferably 0 to 2.5.
- The upper limit and lower limit of a mass ratio [mass of component (d) / mass of component (a)] between the component (d) and the component (a) contained in the monomer group are, for example, 2, 1.5, 1, 0.9, 0.5, 0.2, 0.1, 0.09, 0.05, and 0. In one embodiment, the above mass ratio is preferably 0 to 2.
- The upper limit and lower limit of a mass ratio [mass of component (e) / mass of component (a)] between the component (e) and the component (a) contained in the monomer group are, for example, 1.5, 1, 0.9, 0.5, 0.2, 0.1, 0.09, 0.05, and 0. In one embodiment, the above mass ratio is preferably 0 to 1.5.
- The upper limit and lower limit of a mass ratio [mass of component (c) / mass of component (b)] between the component (c) and the component (b) contained in the monomer group are, for example, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1.5, 1, 0.9, 0.5, 0.2, 0.1, 0.09, 0.05, and 0. In one embodiment, the above mass ratio is preferably 0 to 10.
- The upper limit and lower limit of a mass ratio [mass of component (d) / mass of component (b)] between the component (d) and the component (b) contained in the monomer group are, for example, 8, 7, 6, 5, 4, 3, 2, 1.5, 1, 0.9, 0.5, 0.2, 0.1, 0.09, 0.05, and 0. In one embodiment, the above mass ratio is preferably 0 to 8.
- The upper limit and lower limit of a mass ratio [mass of component (e) / mass of component (b)] between the component (e) and the component (b) contained in the monomer group are, for example, 6, 5, 4, 3, 2, 1.5, 1, 0.9, 0.5, 0.2, 0.1, 0.09, 0.05, and 0. In one embodiment, the above mass ratio is preferably 0 to 6.
- In the above monomer group, monomers (other components) that correspond to none of the components (a) to (e) may be used as long as the desired effects of the disclosure are not impaired. As the other components, various known ones may be used singly or in combination of two or more.
- Examples of the other components include a hydroxyl group-free unsaturated carboxylic ester, a conjugated diene, and an aromatic vinyl compound.
- The hydroxyl group-free unsaturated carboxylic ester is preferably a hydroxyl group-free (meth)acrylic ester. Examples of the hydroxyl group-free (meth)acrylic ester include a hydroxyl group-free linear (meth)acrylic ester, a hydroxyl group-free branched (meth)acrylic ester, a hydroxyl group-free alicyclic (meth)acrylic ester, and a hydroxyl group-free substituted (meth)acrylic ester.
- Examples of the hydroxyl group-free linear (meth)acrylic ester include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, n-amyl (meth)acrylate, hexyl (meth)acrylate, n-octyl (meth)acrylate, nonyl (meth)acrylate, and decyl (meth)acrylate.
- Examples of the hydroxyl group-free branched (meth)acrylic ester include i-propyl (meth)acrylate, i-butyl (meth)acrylate, i-amyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate.
- Examples of the hydroxyl group-free alicyclic (meth)acrylic ester include cyclohexyl (meth)acrylate.
- Examples of the hydroxyl group-free substituted (meth)acrylic ester include glycidyl (meth)acrylate, allyl (meth)acrylate, and ethylene di(meth)acrylate.
- In addition, the above hydroxyl group-free substituted (meth)acrylic ester also includes an alkoxyalkyl (meth)acrylate other than the above alkoxyalkyl (meth)acrylate represented by general formula (1).
- The hydroxyl group-free unsaturated carboxylic ester can be suitably used for the purpose of imparting flexibility to an electrode. From the above viewpoint, the content of the hydroxyl group-free unsaturated carboxylic ester with respect to 100 mol% of the above monomer group is preferably less than 40 mol% (for example, less than 30 mol%, less than 20 mol%, less than 19 mol%, less than 15 mol%, less than 10 mol%, less than 5 mol%, less than 1 mol%, or 0 mol%).
- In addition, the content of the hydroxyl group-free unsaturated carboxylic ester with respect to 100% by mass of the above monomer group is preferably 40% by mass or less (for example, less than 30% by mass, less than 20% by mass, less than 19% by mass, less than 15% by mass, less than 10% by mass, less than 5% by mass, less than 1% by mass, or 0% by mass).
- Examples of the conjugated diene include 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-chloro-1,3-butadiene, a substituted linear conjugated pentadiene, and a substituted and side chain conjugated hexadiene.
- From the viewpoint of cycle characteristics of the lithium-ion battery, the content of the conjugated diene with respect to 100 mol% of the above monomer group is preferably less than 10 mol%, more preferably 0 mol%.
- The upper limit and lower limit of the content of the conjugated diene with respect to 100% by mass of the above monomer group are, for example, 30% by mass, 20% by mass, 10% by mass, 5% by mass, 1% by mass, and 0% by mass. In one embodiment, the above content is preferably 0% by mass to 30% by mass.
- In addition, examples of the aromatic vinyl compound include styrene, α-methylstyrene, p-methylstyrene, vinyltoluene, chlorostyrene, and divinylbenzene.
- From the viewpoint of cycle characteristics of the lithium-ion battery, the content of the aromatic vinyl compound with respect to 100 mol% of the above monomer group is preferably less than 10 mol%, more preferably 0 mol%.
- The upper limit and lower limit of the content of the aromatic vinyl compound with respect to 100% by mass of the above monomer group are, for example, 30% by mass, 20% by mass, 10% by mass, 5% by mass, 1% by mass, and 0% by mass. In one embodiment, the above content is preferably 0% by mass to 30% by mass.
- A ratio of the other components than the hydroxyl group-free unsaturated carboxylic ester, the conjugated diene and the aromatic vinyl compound mentioned above in the above monomer group is, for example, less than 10 mol%, less than 5 mol%, less than 2 mol%, less than 1 mol%, less than 0.1 mol%, less than 0.01 mol%, or 0 mol%, with respect to 100 mol% of the above monomer group. In addition, with respect to 100% by mass of the above monomer group, the ratio of the other components is, for example, less than 10% by mass, less than 9% by mass, less than 7% by mass, less than 5% by mass, less than 4% by mass, less than 2% by mass, less than 1% by mass, less than 0.9% by mass, less than 0.5% by mass, less than 0.3% by mass, less than 0.1% by mass, less than 0.05% by mass, less than 0.01% by mass, or 0% by mass.
- The component (A) may be synthesized by various known polymerization methods, preferably a radical polymerization method. Specifically, it is preferable to add a radical polymerization initiator and, if necessary, a chain transfer agent, to a monomer mixture containing the aforementioned components, and, while stirring the mixture, perform a polymerization reaction at a reaction temperature of 50 °C to 100 °C. The reaction time is not particularly limited and is preferably 1 hour to 10 hours.
- As the radical polymerization initiator, various known ones may be used without particular limitation. Examples of the radical polymerization initiator include: a persulfate, such as potassium persulfate and ammonium persulfate; a redox polymerization initiator in which the above persulfate and a reductant such as sodium bisulfite are combined; and an azo initiator, such as 2,2'-azobis-2-amidinopropane dihydrochloride. The amount of the radical polymerization initiator used is not particularly limited, and is preferably 0.05% by mass to 5.0% by mass, more preferably 0.1% by mass to 3.0% by mass, with respect to 100% by mass of the monomer group that provides the component (A).
- Before the radical polymerization reaction and/or when the obtained component (A) is dissolved in water, for the purpose of improving production stability, the pH of a reaction solution may be adjusted by a general neutralizer such as ammonia or organic amine, potassium hydroxide, sodium hydroxide, and lithium hydroxide. In this case, the pH is preferably 2 to 11. For the same purpose, it is also possible to use ethylene diamine tetraacetic acid (EDTA), which is a metal ion sealant, or a salt thereof, or the like.
- If the component (A) has an acid group, it can be used by a neutralization ratio thereof being appropriately adjusted (a neutralization ratio of 100% indicating that neutralization is performed by an alkali having the same number of moles as the acid component contained in the component (A); a neutralization ratio of 50% indicating that neutralization is performed by an alkali having half the number of moles of the acid component contained in the component (A)) depending on the use. The neutralization ratio when the electrode active material is dispersed is not particularly limited. In one embodiment, the neutralization ratio is preferably 95% to 100% after formation of a coating layer or the like. 95% or more is preferable from the viewpoint of preventing a decrease in initial capacity, and 100% or less is preferable from the viewpoint of preventing hydrolysis. Examples of a neutralized salt include Li salt, Na salt, K salt, ammonium salt, Mg salt, Ca salt, Zn salt, and Al salt.
- In one embodiment, the component (A) is preferably an inorganic salt. The inorganic salt as the component (A) refers to a salt whose cationic portion is a metal cation. Examples of the inorganic salt include those mentioned above.
- The upper limit and lower limit of a glass transition temperature of the component (A) are, for example, 160 °C, 155 °C, 150 °C, 145 °C, 140 °C, 135 °C, 130 °C, 125 °C, 120 °C, 115 °C, 110 °C, 105 °C, 100 °C, 95 °C, 90 °C, 85 °C, 80 °C, 75 °C, 70 °C, 65 °C, 60 °C, 55 °C, 50 °C, 45 °C, 40 °C, 35 °C, 30 °C, 25 °C, 20 °C, 15 °C, 10 °C, 5 °C, and 0 °C. In one embodiment, 0 °C or higher is preferable, and 30 °C or higher is more preferable from the viewpoints of mechanical strength and heat resistance.
- The glass transition temperature of the component (A) may be adjusted by a combination of monomers. The glass transition temperature of the component (A) can be calculated from glass transition temperatures (Tg) (absolute temperature: K) of homopolymers of the monomers and mass fractions thereof based on the Fox equation shown below.
- For example, the glass transition temperature is 165 °C in the case of a homopolymer of acrylamide, is 106 °C in the case of a homopolymer of acrylic acid, is -15 °C in the case of a homopolymer of hydroxyethyl acrylate, and is 105 °C in the case of a homopolymer of acrylonitrile. In order to obtain the component (A) having a desired glass transition temperature, the monomer composition constituting the component (A) can be determined. Moreover, the glass transition temperature of a homopolymer of a monomer can be measured by a differential scanning calorimeter (DSC), a differential thermal analyzer (DTA), a thermomechanical measurement apparatus (TMA) or the like under the condition that the temperature is raised from -100 °C to 300 °C (at a temperature rising rate of 10 °C/min). Moreover, values described in a literature may also be used. Examples of the literature include page 325 of "Handbook of Chemistry: Pure Chemistry II" (Revised 5th Edition) edited by the Chemical Society of Japan.
- A weight average molecular weight (Mw) of the component (A) is not particularly limited, and its upper limit and lower limit are, for example, 7,000,000, 6,500,000, 6,000,000, 5,500,000, 5,000,000, 4,500,000, 4,000,000, 3,500,000, 3,000,000, 2,500,000, 2,000,000, 1,500,000, 1,000,000, 950,000, 900,000, 850,000, 800,000, 750,000, 700,000, 650,000, 600,000, 550,000, 500,000, 450,000, 400,000, 350,000, 300,000, 250,000, 200,000, 150,000, and 100,000. In one embodiment, from the viewpoint of dispersion stability of slurry, 100,000 to 7,000,000 are preferable, and 350,000 to 6,000,000 are more preferable.
- A number average molecular weight (Mn) of the component (A) is not particularly limited, and its upper limit and lower limit are, for example, 6,000,000, 5,500,000, 5,000,000, 4,500,000, 4,000,000, 3,500,000, 3,000,000, 2,500,000, 2,000,000, 1,500,000, 1,000,000, 950,000, 900,000, 850,000, 800,000, 750,000, 700,000, 650,000, 600,000, 550,000, 500,000, 450,000, 400,000, 300,000, 200,000, 100,000, 50,000, and 10,000. In one embodiment, the number average molecular weight (Mn) of the component (A) is preferably 10,000 or more.
- The weight average molecular weight and the number average molecular weight may be calculated, for example, as values in terms of polyacrylic acid as measured by gel permeation chromatography (GPC) in an appropriate solvent.
- The upper limit and lower limit of a molecular weight distribution (Mw/Mn) of the component (A) are, for example, 15, 14, 13, 11, 10, 9, 7.5, 5, 4, 3, 2.9, 2.5, 2, 1.5, and 1.1. In one embodiment, the molecular weight distribution (Mw/Mn) of the component (A) is preferably 1.1 to 15.
- B-type viscosity of an aqueous solution containing 13% by mass of the component (A) is not particularly limited, and its upper limit and lower limit are, for example, 100,000 mPa·s, 90,000 mPa·s, 80,000 mPa·s, 70,000 mPa·s, 60,000 mPa·s, 50,000 mPa·s, 45,000 mPa·s, 40,000 mPa·s, 30,000 mPa·s, 20,000 mPa·s, 10,000 mPa·s, 9,000 mPa·s, 8,000 mPa·s, 7,000 mPa·s, 6,000 mPa·s, 5,000 mPa·s, 4,000 mPa·s, 3,000 mPa·s, 2,000 mPa·s, 1,000 mPa·s, 900 mPa·s, 700 mPa·s, 500 mPa·s, 300 mPa·s, 200 mPa·s, and 100 mPa·s. In one embodiment, the above B-type viscosity preferably ranges from 100 mPa·s to 100,000 mPa·s.
- The B-type viscosity is measured by a B-type viscometer such as "B-type Viscometer Model BM" (product name) made by Toki Sangyo Co., Ltd.
- The upper limit and lower limit of the pH of the binder aqueous solution for a lithium-ion battery are, for example, 9, 8.9, 8.5, 8, 7.9, 7.5, 7, 6.9, 6.5, 6, 5.9, 5.6, 5.5, 5.4, 5.2, 5.1, 5, and 4. In one embodiment, the pH of the binder aqueous solution for a lithium-ion battery is preferably 4 to 9 and more preferably 4 to 7 from the viewpoint of solution stability.
- The pH may be measured at 25 °C using a glass electrode pH meter (for example, "Handy pH Meter D-52" (product name) made by Horiba, Ltd.).
- The upper limit and lower limit of the content of the component (A) with respect to 100% by mass of the binder aqueous solution for a lithium-ion battery are, for example, 20% by mass, 19% by mass, 15% by mass, 14% by mass, 12% by mass, 10% by mass, 9% by mass, 7% by mass, 6% by mass, and 5% by mass. In one embodiment, the content of the component (A) with respect to 100% by mass of the binder aqueous solution for a lithium-ion battery is preferably 5% by mass to 20% by mass.
- The upper limit and lower limit of the content of water with respect to 100% by mass of the binder aqueous solution for a lithium-ion battery are, for example, 95% by mass, 90% by mass, 85% by mass, and 80% by mass. In one embodiment, the content of the water with respect to 100% by mass of the binder aqueous solution for a lithium-ion battery is preferably 80% by mass to 95% by mass.
- The upper limit and lower limit of a mass ratio between the component (A) and the water contained in the binder aqueous solution for a lithium-ion battery are, for example, 0.25, 0.2, 0.15, 0.1, and 0.05. In one embodiment, the mass ratio between the component (A) and the water contained in the binder aqueous solution for a lithium-ion battery is preferably 0.05 to 0.25.
- In one embodiment, the above binder aqueous solution for a lithium-ion battery contains a dispersion (emulsion).
- Examples of the dispersion (emulsion) include styrene-butadiene-based copolymer latex, polystyrene-based polymer latex, polybutadiene-based polymer latex, acrylonitrile-butadiene-based copolymer latex, polyurethane-based polymer latex, polymethylmethacrylate-based polymer latex, methylmethacrylate-butadiene-based copolymer latex, polyacrylate-based polymer latex, vinyl chloride-based polymer latex, vinyl acetate-based polymer emulsion, vinyl acetate-ethylene-based copolymer emulsion, polyethylene emulsion, carboxy-modified styrene-butadiene copolymer resin emulsion, acrylic resin emulsion, polyethylene, polypropylene, polyethylene terephthalate, polyamide (PA), polyimide (PI), polyamide-imide (PAI), an aromatic polyamide, alginic acid and a salt thereof, polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), a tetrafluoroethylene-hexafluoropropylene copolymer (FEP), a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), and an ethylene tetrafluoroethylene (ETFE) copolymer.
- The upper limit and lower limit of the content of the dispersion (emulsion) with respect to 100% by mass of the component (A) are, for example, 50% by mass, 45% by mass, 40% by mass, 35% by mass, 30% by mass, 25% by mass, 20% by mass, 19% by mass, 17% by mass, 15% by mass, 13% by mass, 10% by mass, 9% by mass, 7% by mass, 5% by mass, 4% by mass, 2% by mass, 1% by mass, and 0% by mass. In one embodiment, from the viewpoints of springback resistance and discharge capacity retention rate, the amount of the dispersion (emulsion) added with respect to 100% by mass of the component (A) is preferably 0% by mass to 50% by mass.
- The binder aqueous solution for a lithium-ion battery may contain, as an additive, a component that does not correspond to any of the component (A), water, and the dispersion (emulsion).
- Examples of the additive include a dispersant, a leveling agent, an antioxidant, and a thickener.
- The content of the additive is, for example, 0% by mass to 5% by mass, less than 1% by mass, less than 0.1% by mass, less than 0.01% by mass, or 0% by mass, with respect to 100% by mass of the component (A). In one embodiment, the content of the additive is preferably 5% by mass or less with respect to 100% by mass of the component (A) from the viewpoint that haze is generated in the binder when the content exceeds 5% by mass.
- In addition, the content of the additive is, for example, 0% by mass to 5% by mass, less than 1% by mass, less than 0.1% by mass, less than 0.01% by mass, or 0% by mass, with respect to 100% by mass of the above aqueous solution.
- Examples of the dispersant include an anionic dispersant, a cationic dispersant, a nonionic dispersant, and a polymer dispersant.
- Examples of the leveling agent include a surfactant, such as an alkyl-based surfactant, a silicon-based surfactant, a fluorine-based surfactant, and a metal-based surfactant. By using the surfactant, cissing that occurs during coating may be prevented and smoothness of a slurry layer (coating layer) may be improved.
- Examples of the antioxidant include a phenol compound, a hydroquinone compound, an organophosphorus compound, a sulfur compound, a phenylenediamine compound, and a polymer type phenol compound. The polymer type phenol compound is a polymer having a phenol structure in a molecule. A weight average molecular weight of the polymer type phenol compound is preferably 200 to 1,000, more preferably 600 to 700.
- Examples of the thickener include: a cellulosic polymer, such as carboxymethyl cellulose, methyl cellulose, and hydroxypropyl cellulose, as well as an ammonium salt and an alkali metal salt thereof; (modified) poly(meth)acrylic acid as well as an ammonium salt and an alkali metal salt thereof; polyvinyl alcohols, such as (modified) polyvinyl alcohol, a copolymer of acrylic acid or acrylate and vinyl alcohol, a copolymer of maleic anhydride, maleic acid, or fumaric acid and vinyl alcohol; polyethylene glycol, polyethylene oxide, polyvinylpyrrolidone, modified polyacrylic acid, oxidized starch, phosphoric acid starch, casein, various modified starches, and an acrylonitrile-butadiene copolymer hydride.
- The binder aqueous solution for a lithium-ion battery may be used as a binder aqueous solution for a lithium-ion battery electrode, or a binder aqueous solution for a lithium-ion battery negative electrode.
- The disclosure provides a slurry for a lithium-ion battery negative electrode, the slurry containing the above binder aqueous solution for a lithium-ion battery and a negative electrode active material (B).
- In the disclosure, "slurry" means a suspension of liquid and solid particles.
- The upper limit and lower limit of the content of the component (A) with respect to 100% by mass of the above slurry are, for example, 99.9% by mass, 95% by mass, 90% by mass, 80% by mass, 70% by mass, 60% by mass, 50% by mass, 40% by mass, 30% by mass, 20% by mass, 10% by mass, 5% by mass, 1% by mass, 0.5% by mass, 0.2% by mass, and 0.1% by mass. In one embodiment, the content of the component (A) is preferably 0.1% by mass to 99.9% by mass with respect to 100% by mass of the above slurry.
- Examples of the water include ultrapure water, pure water, distilled water, ion-exchanged water, and tap water.
- The upper limit and lower limit of the content of the water with respect to 100% by mass of the above slurry are, for example, 70% by mass, 65% by mass, 60% by mass, 55% by mass, 50% by mass, 45% by mass, 40% by mass, 35% by mass, and 30% by mass. In one embodiment, the content of the water is preferably 30% by mass to 70% by mass with respect to 100% by mass of the above slurry.
- A negative electrode active material may be used singly or in combination of two or more.
- The negative electrode active material is not particularly limited as long as being capable of reversibly occluding and releasing lithium, and an appropriate material may be suitably selected depending on the type of the target lithium-ion battery. The negative electrode active material may be used singly or in combination of two or more. Examples of the negative electrode active material include a carbon material, as well as a material alloyable with lithium, such as a silicon material, a lithium atom-containing oxide, a lead compound, a tin compound, an arsenic compound, an antimony compound, and an aluminum compound.
- Examples of the above carbon material include graphite (for example, natural graphite and artificial graphite) which is highly crystalline carbon, low crystalline carbon (such as soft carbon and hard carbon), carbon black (such as Ketjen black, acetylene black, channel black, lamp black, oil furnace black, and thermal black), a fullerene, a carbon nanotube, a carbon nanofiber, a carbon nanohorn, a carbon fibril, mesocarbon microbeads (MCMB), and a pitch-based carbon fiber.
- Examples of the above silicon material include, in addition to silicon, silicon oxide and silicon alloy, silicon oxide composites expressed by SiC, SiOxCy (in which 0<x≦3, and 0<y≦5), Si3N4, Si2N2O, and SiOx (in which 0<x≦2) (for example, materials described in Japanese Patent Laid-Open Nos.
2004-185810 2005-259697 2004-185810 5390336 5903761 - The above silicon oxide is preferably a silicon oxide expressed by a composition formula SiOx (in which 0<x<2, preferably 0.1≦x≦1).
- The above silicon alloy is preferably an alloy of silicon and at least one transition metal selected from the group consisting of titanium, zirconium, nickel, copper, iron and molybdenum. Silicon alloys of these transition metals are preferable due to high electronic conductivity and high strength. The silicon alloy is more preferably a silicon-nickel alloy or a silicon-titanium alloy, particularly preferably a silicon-titanium alloy. A content ratio of silicon in the silicon alloy is preferably 10 mol% or more, more preferably 20 mol% to 70 mol%, with respect to 100 mol% of metal elements in the above silicon alloy. The silicon material may be single crystalline, polycrystalline, or amorphous.
- When the silicon material is used as the negative electrode active material, a negative electrode active material other than the silicon material may be used together. Examples of such a negative electrode active material include the above carbon material; a conductive polymer such as polyacene; a composite metal oxide expressed by AXBYOZ (in which A represents an alkali metal or a transition metal, B represents at least one selected from transition metals such as cobalt, nickel, aluminum, tin, and manganese, O represents an oxygen atom, and X, Y, and Z are respectively numbers in the following ranges: 0.05<X<1.10, 0.85<Y<4.00 and 1.5<Z<5.00), or other metal oxide. When the silicon material is used as the negative electrode active material, it is preferable to use a carbon material together because a volume change associated with the occlusion and release of lithium is small.
- Examples of the above lithium atom-containing oxide include a ternary nickel cobalt lithium manganate, a lithium-transition metal composite oxide, such as a lithium-manganese composite oxide (such as LiMn2O4), a lithium-nickel composite oxide (such as LiNiO2), a lithium-cobalt composite oxide (such as LiCoO2), a lithium-iron composite oxide (such as LiFeO2), a lithium-nickel-manganese composite oxide (such as LiNi0.5Mn0.5O2), a lithium-nickel-cobalt composite oxide (such as LiNi0.8Co0.2O2), a lithium-transition metal phosphate compound (such as LiFePO4), a lithium-transition metal sulfate compound (such as LixFe2(SO4)3), a lithium-titanium composite oxide (such as lithium titanate: Li4Ti5O12), and other conventionally known negative electrode active materials.
- From the viewpoint of remarkably exhibiting the effect of the disclosure, the carbon material and/or the material alloyable with lithium is preferably contained in the negative electrode active material in an amount of 50% by mass or more, more preferably 80% by mass or more, further preferably 90% by mass or more, and particularly preferably 100% by mass.
- In one embodiment, the negative electrode active material (B) is preferably a negative electrode active material containing 1% by mass or more (for example, 2% by mass or more, 5% by mass or more, 10% by mass or more, 25% by mass or more, 50% by mass or more, 75% by mass or more, 90% by mass or more, or 100% by mass) of silicon and/or a silicon oxide covered with a carbon layer.
- The shape of the negative electrode active material is not particularly limited and may be an arbitrary shape such as a fine particle shape or a thin film shape, and a fine particle shape is preferable. An average particle diameter of the negative electrode active material is not particularly limited, and its upper limit and lower limit are, for example, 50 µm, 45 µm, 40 µm, 35 µm, 30 µm, 25 µm, 20 µm, 15 µm, 10 µm, 5 µm, 4 µm, 3 µm, 2.9 µm, 2 µm, 1 µm, 0.5 µm, and 0.1 µm. In one embodiment, from the viewpoint of forming a uniform and thin coating film, more specifically, for the reason that handleability is good if the average particle diameter is 0.1 µm or more and application of an electrode is easy if the average particle diameter is 50 µm or less, the average particle diameter of the negative electrode active material is preferably 0.1 µm to 50 µm, more preferably 0.1 µm to 45 µm, further preferably 1 µm to 10 µm, and particularly preferably 5 µm.
- In the disclosure, "particle diameter" means a maximum distance among distances between arbitrary two points on a contour line of a particle (the same applies hereinafter). In addition, in the disclosure, unless otherwise specified, "average particle diameter" means a value calculated as an average value of particle diameters of particles observed in several to several tens of visual fields using an observation means such as a scanning electron microscope (SEM) or a transmission electron microscope (TEM) (the same applies hereinafter).
- The upper limit and lower limit of the content of the component (A) in the above slurry with respect to 100% by mass of the negative electrode active material (B) are, for example, 15% by mass, 14% by mass, 13% by mass, 12% by mass, 11% by mass, 10% by mass, 9% by mass, 8% by mass, 7% by mass, 6% by mass, 5% by mass, 4% by mass, 3% by mass, 2% by mass, 1.5% by mass, 1% by mass, and 0.5 mass%. In one embodiment, the above content is preferably 0.5% by mass to 15% by mass.
- In one embodiment, a conductive aid may be contained in the above slurry. Examples of the conductive aid include fibrous carbon such as vapor grown carbon fiber (VGCF), a carbon nanotube (CNT) and carbon nanofiber (CNF), carbon black such as graphite particles, acetylene black, Ketjen black and furnace black, and fine powders of Cu, Ni, Al, Si or alloys thereof having an average particle diameter of 10 µm or less. The content of the conductive aid is not particularly limited, and is preferably 0% by mass to 10% by mass, more preferably 0.5% by mass to 6% by mass, with respect to the negative electrode active material component.
- A slurry viscosity adjustment solvent is not particularly limited, and may include a non-aqueous medium having a normal boiling point of 80 °C to 350 °C. The slurry viscosity adjustment solvent may be used singly or in combination of two or more. Examples of the slurry viscosity adjustment solvent include: an amide solvent, such as N-methylpyrrolidone, dimethylformamide, and N,N-dimethylacetamide; a hydrocarbon solvent, such as toluene, xylene, n-dodecane, and tetralin; an alcohol solvent, such as methanol, ethanol, 2-propanol, isopropyl alcohol, 2-ethyl-1-hexanol, 1-nonanol, and lauryl alcohol; a ketone solvent, such as acetone, methyl ethyl ketone, cyclohexanone, phorone, acetophenone, and isophorone; an ether solvent, such as dioxane and tetrahydrofuran (THF); an ester solvent, such as benzyl acetate, isopentyl butyrate, methyl lactate, ethyl lactate, and butyl lactate; an amine solvent, such as o-toluidine, m-toluidine, and p-toluidine; a lactone, such as γ-butyrolactone and δ-butyrolactone; a sulfoxide and sulfone solvent, such as dimethyl sulfoxide and sulfolane; and water. Among them, N-methylpyrrolidone is preferable from the viewpoint of application workability. The content of the above non-aqueous medium is not particularly limited, and is preferably 0% by mass to 10% by mass with respect to 100% by mass of the above slurry.
- The above slurry may contain, as an additive, a component that does not correspond to any of the component (A), the component (B), water, the conductive aid, and the slurry viscosity adjustment solvent without impairing the effects of the disclosure. Examples of the additive include those described above.
- The content of the additive is, for example, 0% by mass to 5% by mass, less than 1% by mass, less than 0.1% by mass, less than 0.01% by mass, or 0% by mass, with respect to 100% by mass of the component (A).
- The content of the additive with respect to 100% by mass of the component (B) is, for example, 0% by mass to 5% by mass, less than 1% by mass, less than 0.1% by mass, less than 0.01% by mass, or 0% by mass.
- Moreover, the dispersion (emulsion) may be contained in a larger amount than the above additive content. The upper limit and lower limit of the content of the dispersion (emulsion) with respect to 100% by mass of the slurry for a lithium-ion battery negative electrode are, for example, 20% by mass, 19% by mass, 17% by mass, 15% by mass, 13% by mass, 10% by mass, 9% by mass, 7% by mass, 5% by mass, 4% by mass, 2% by mass, 1% by mass, and 0% by mass. In one embodiment, from the viewpoints of springback resistance and discharge capacity retention rate, the amount of the dispersion (emulsion) added with respect to 100% by mass of the above aqueous solution or the slurry for a lithium-ion battery negative electrode is preferably less than 5% by mass.
- The above slurry is prepared by mixing the component (A), the component (B), water, and if necessary, the conductive aid and the slurry viscosity adjustment solvent.
- Examples of a means of mixing the slurry include a ball mill, a sand mill, a pigment disperser, a Raikai mixer, an ultrasonic disperser, a homogenizer, a planetary mixer, and a Hobart mixer.
- The disclosure provides a negative electrode for a lithium-ion battery, obtained by applying the above slurry for a lithium-ion battery negative electrode to a current collector, and drying and curing the slurry. The above lithium-ion battery negative electrode has a cured product of the above slurry for a lithium-ion battery negative electrode on a surface of the current collector.
- As the current collector, various known ones may be used without particular limitation. A material of the current collector is not particularly limited, and examples thereof include a metal material, such as copper, iron, aluminum, nickel, stainless steel, and nickel-plated steel, or a carbon material, such as carbon cloth and carbon paper. The form of the current collector is not particularly limited. In the case of metal material, examples thereof include a metal foil, a metal cylinder, a metal coil, and a metal plate; in the case of carbon material, examples thereof include a carbon plate, a carbon thin film, and a carbon cylinder. Among them, when an electrode active material is used in the negative electrode, a copper foil is preferably used as the current collector because it is currently used in industrialized products.
- The application means is not particularly limited, and examples thereof include a conventionally known coating device, such as a comma coater, a gravure coater, a micro gravure coater, a die coater, and a bar coater.
- The drying means is also not particularly limited, and the temperature is preferably 60 °C to 200 °C, more preferably 100 °C to 195 °C. The atmosphere may be dry air or an inert atmosphere.
- The thickness of the negative electrode (cured product) is not particularly limited, and is preferably 5 µm to 300 µm, more preferably 10 µm to 250 µm. By setting the above range, a function of occluding and releasing sufficient lithium with respect to a high-density current value may be easily obtained.
- The disclosure provides a lithium-ion battery including the above negative electrode for a lithium-ion battery. In one embodiment, the above battery includes an electrolyte solution, a separator, a positive electrode and so on. The above are not particularly limited.
- Examples of the electrolyte solution include non-aqueous electrolytic solution in which a supporting electrolyte is dissolved in a non-aqueous solvent. In addition, a film forming agent may be contained in the above non-aqueous electrolytic solution.
- As the non-aqueous solvent, various known ones may be used without particular limitation, and may be used singly or in combination of two or more. Examples of the non-aqueous solvent include: a chain carbonate solvent, such as diethyl carbonate, dimethyl carbonate, and ethyl methyl carbonate; a cyclic carbonate solvent, such as ethylene carbonate, propylene carbonate, and butylene carbonate; a chain ether solvent, such as 1,2-dimethoxyethane; a cyclic ether solvent, such as tetrahydrofuran, 2-methyltetrahydrofuran, sulfolane, and 1,3-dioxolane; a chain ester solvent, such as methyl formate, methyl acetate, and methyl propionate; a cyclic ester solvent, such as γ-butyrolactone and γ-valerolactone; and acetonitrile. Among them, a combination of mixed solvents containing a cyclic carbonate and a chain carbonate is preferable.
- A lithium salt is used as the supporting electrolyte. As the lithium salt, various known ones may be used without particular limitation, and may be used singly or in combination of two or more. Examples of the supporting electrolyte include LiPF6, LiAsF6, LiBF4, LiSbF6, LiAlCl4, LiClO4, CF3SO3Li, C4F9SO3Li, CF3COOLi, (CF3CO)2NLi, (CF3SO2)2NLi, and (C2F5SO2)NLi. Among them, LiPF6, LiClO4 and CF3SO3Li, which are easily dissolved in a solvent and exhibit a high dissociation degree, are preferable. The higher the dissociation degree of the supporting electrolyte, the higher the lithium-ion conductivity. Therefore, the lithium-ion conductivity can be adjusted according to the type of the supporting electrolyte.
- As the film forming agent, various known ones may be used without particular limitation, and may be used singly or in combination of two or more. Examples of the film forming agent include: a carbonate compound, such as vinylene carbonate, vinyl ethylene carbonate, vinyl ethyl carbonate, methylphenyl carbonate, fluoroethylene carbonate, and difluoroethylene carbonate; an alkene sulfide, such as ethylene sulfide and propylene sulfide; a sultone compound, such as 1,3-propane sultone and 1,4-butane sultone; and an acid anhydride, such as maleic anhydride and succinic anhydride. The content of the film forming agent in the electrolyte solution is not particularly limited, and is 10% by mass or less, 8% by mass or less, 5% by mass or less, or 2% by mass or less, in order of preference. By setting the content to 10% by mass or less, the advantages of the film forming agent, such as suppression of initial irreversible capacity or improvement in low temperature characteristics and rate characteristics, may be easily achieved.
- The separator is an article interposed between a positive electrode and a negative electrode, and is used to prevent a short circuit between the electrodes. Specifically, a porous separator such as a porous film or a nonwoven fabric may be preferably used, which is impregnated with the aforementioned non-aqueous electrolytic solution for use. As a material of the separator, a polyolefin such as polyethylene and polypropylene, or polyethersulfone, is used, and polyolefin is preferable.
- As the positive electrode, various known ones may be used without particular limitation. Examples of the positive electrode include one obtained by preparing a slurry by mixing a positive electrode active material, a conductive aid, and a binder for a positive electrode with an organic solvent, applying the prepared slurry to a positive electrode current collector and drying and pressing.
- Examples of the positive electrode active material include an inorganic positive electrode active material and an organic positive electrode active material. Examples of the inorganic positive electrode active material include a transition metal oxide, a composite oxide of lithium and a transition metal, and a transition metal sulfide. Examples of the above transition metal include Fe, Co, Ni, Mn, and Al. Examples of the inorganic compound used in the positive electrode active material include: a lithium-containing composite metal oxide, such as LiCoO2, LiNiO2, LiMnO2, LiMn2O4, LiFePO4, LiNi1/2Mn3/2O4, LiCo1/3Ni1/3Mn1/3O2, Li[Li0.1Al0.1Mn1.8]O4, and LiFeVO4; a transition metal sulfide, such as TiS2, TiS3, and amorphous MoS2; and a transition metal oxide, such as Cu2V2O3, amorphous V2O-P2O5, MoO3, V2O5, and V6O13. These compounds may be partially element-substituted. Examples of the organic positive electrode active material include a conductive polymer, such as polyacetylene and poly-p-phenylene. An iron-based oxide having poor electric conductivity may be used as an electrode active material covered with a carbon material by allowing a carbon source material to exist during reduction firing. These compounds may be partially element-substituted. Among them, from the viewpoints of practicality, electrical characteristics and long life, LiCoO2, LiNiO2, LiMnO2, LiMn2O4, LiFePO4, LiNi1/2Mn3/2O4, LiCo1/3Ni1/3Mn1/3O2, and Li[Li0.1Al0.1Mn1.8]O4 are preferable.
- Examples of the conductive aid include fibrous carbon such as vapor grown carbon fiber (VGCF), a carbon nanotube (CNT) and carbon nanofiber (CNF), carbon black such as graphite particles, acetylene black, Ketjen black and furnace black, and fine powders of Cu, Ni, Al, Si or alloys thereof having an average particle diameter of 10 µm or less.
- As the binder for a positive electrode, various known ones may be used without particular limitation, and may be used singly or in combination of two or more thereof. Examples of the binder for a positive electrode include a fluorine-based resin (such as polyvinylidene fluoride and polytetrafluoroethylene), a polyolefin (such as polyethylene and polypropylene), a polymer having an unsaturated bond (such as styrene-butadiene rubber, isoprene rubber, and butadiene rubber), and an acrylic acid-based polymer (such as an acrylic acid copolymer and a methacrylic acid copolymer).
- Examples of the positive electrode current collector include an aluminum foil and a stainless steel foil.
- The form of the above lithium-ion battery is not particularly limited. Examples of the form of the lithium-ion battery include a cylinder type in which a sheet electrode and a separator are formed in a spiral shape, a cylinder type having an inside-out structure in which a pellet electrode and a separator are combined, and a coin type in which a pellet electrode and a separator are laminated. In addition, by accommodating the battery of these forms in an arbitrary exterior case, the battery can be used in an arbitrary shape such as a coin shape, a cylindrical shape, and a square shape.
- A method for producing the above lithium-ion battery is not particularly limited, and the lithium-ion battery may be assembled by an appropriate procedure depending on the structure of the battery. Examples of the method for producing a lithium-ion battery include a method described in Japanese Patent Laid-Open No.
2013-089437 - Hereinafter, the disclosure will be specifically described through examples and comparative examples. However, the above description of the preferred embodiments and the following examples are provided for illustration only and not for limiting the disclosure. Therefore, the scope of the disclosure is not limited to the embodiments or examples specifically described herein, but only by the claims. In addition, in each of the examples and comparative examples, unless otherwise specified, numerical values such as part and % are based on mass.
- In a reactor equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen gas introduction pipe, 1,240 g of ion-exchanged water, 350 g (2.46 mol) of 50% acrylamide aqueous solution, 56.6 g (0.43 mol) of 2-methoxyethyl acrylate, and 0.23 g (0.0014 mol) of sodium methallyl sulfonate were put, and after oxygen in the reaction system was removed through nitrogen gas, the resultant was heated to 55 °C. 2.1 g of 2,2'-azobis-2-amidinopropane dihydrochloride (product name "NC-32" made by NIPPOH CHEMICALS CO., LTD.) and 20 g of ion-exchanged water were put therein, and the resultant was heated to 80 °C and reacted for 3 hours. Ion-exchanged water was added so as to achieve a solid content concentration of 13%, and a binder aqueous solution containing a water-soluble poly(meth)acrylamide was obtained. The B-type viscosity of this solution at 25 °C was 10,000 mPa·s.
- In Preparation Examples 2 to 4, a binder aqueous solution containing a water-soluble poly(meth)acrylamide was prepared in the same manner as in Preparation Example 1 except that the monomer composition was changed to those shown in the following table.
- In a reactor equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen gas introduction pipe, 1,170 g of ion-exchanged water, 120 g (0.84 mol) of 50% acrylamide aqueous solution, 12 g (0.12 mol) of N,N-dimethylacrylamide, 62.8 g (0.48 mol) of 2-methoxyethyl acrylate, 87 g (0.96 mol) of 80% acrylic acid and 0.19 g (0.0012 mol) of sodium methallyl sulfonate were put, and after oxygen in the reaction system was removed through nitrogen gas, the resultant was heated to 55 °C. 1.8 g of 2,2'-azobis-2-amidinopropane dihydrochloride (product name "NC-32" made by NIPPOH CHEMICALS CO., LTD.) and 20 g of ion-exchanged water were put therein, and the resultant was heated to 80 °C and reacted for 3 hours. After that, 64.4 g (0.77 mol) of 48% sodium hydroxide aqueous solution as a neutralizer was added and stirred, ion-exchanged water was added so as to achieve a solid content concentration of 13%, and a binder aqueous solution containing a water-soluble poly(meth)acrylamide was obtained. The B-type viscosity of this solution at 25 °C was 12,000 mPa·s.
- In Preparation Examples 6 to 7, a binder aqueous solution containing a water-soluble poly(meth)acrylamide was prepared in the same manner as in Preparation Example 5 except that the monomer composition and the amount of the neutralizer were changed to those shown in the following table.
- In a reactor equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen gas introduction pipe, 1,280 g of ion-exchanged water, 500 g (3.52 mol) of 50% acrylamide aqueous solution, and 0.28 g (0.0018 mol) of sodium methallyl sulfonate were put, and after oxygen in the reaction system was removed through nitrogen gas, the resultant was heated to 55 °C. 2.3 g of 2,2'-azobis-2-amidinopropane dihydrochloride (product name "NC-32" made by NIPPOH CHEMICALS CO., LTD.) and 20 g of ion-exchanged water were put therein, and the resultant was heated to 80 °C and reacted for 3 hours. After that, ion-exchanged water was added so as to achieve a solid content concentration of 13%, and a binder aqueous solution containing a water-soluble poly(meth)acrylamide was obtained. The B-type viscosity of this solution at 25 °C was 15,000 mPa·s.
- In the comparative preparation examples other than Comparative Preparation Example 1, a binder aqueous solution containing a water-soluble poly(meth)acrylamide was prepared in the same manner as in Comparative Preparation Example 1 except that the monomer composition and the like in Comparative Preparation Example 1 were changed to those shown in the following table.
- The viscosity of each binder aqueous solution was measured at 25 °C under the following conditions using a B-type viscometer (product name "B-type Viscometer Model BM" made by Toki Sangyo Co., Ltd.).
- No. 3 rotor was used at a rotational speed of 6 rpm.
- The weight average molecular weight was calculated as a value in terms of polyacrylic acid as measured by gel permeation chromatography (GPC) under a 0.2 M phosphate buffer/acetonitrile solution (90/10, PH 8.0). HLC-8220 (made by Tosoh Corporation) was used as a GPC device, and SB-806M-HQ (made by SHODEX) was used as a column.
[Table 2] (Meth)acrylamide group-containing compound (a) Alkoxyalkyl (meth)acrylate (b) Copolymerizable monomer Neutralizer (amount with respect to acid component) B-type viscosity (mPa·s) Molecular weight (Mw) Unsaturated organic acid or salt thereof (c) Hydroxyalkyl(meth)acrylate (d) having hydroxyalkyl group having 2 to 4 carbon atoms α,β-unsaturated nitrile (e) Other components AM DMAA MEA MMEA MEEA AA SMAS HEA AN BA NaOH (mol%) (mol%) (mol%) (mol%) (mol%) (mol%) (mol%) (mol%) (mol%) (mol%) (mol%) Preparation Example 1 84.95 - 15 - - - 0.05 - - - - 10,000 550,000 Preparation Example 2 69.95 - 30 - - - 0.05 - - - - 5,000 500,000 Preparation Example 3 84.95 - - 15 - - 0.05 - - - - 7,000 500,000 Preparation Example 4 84.95 - - - 15 - 0.05 - - - - 6,000 500,000 Preparation Example 5 34.95 5 20 - - 40 0.05 - - - 80 12,000 850,000 Preparation Example 6 45 - 15 - - 35 0.10 5 - - 90 3,000 600,000 Preparation Example 7 60 - 6 - - 20 - - 14 - 80 10,000 700,000 Comparative Preparation Example 1 99.95 - - - - - 0.05 - - - - 15,000 600,000 Comparative Preparation Example 2 39.95 - 60 - - - 0.05 - - - - Insolubilized (separated into two phases) - Comparative Preparation Example 3 - - 20 - - 79.95 0.05 - - - 90 2,000 400,000 Comparative Preparation Example 4 79.9 - - - - - 0.10 20 - - - 4,000 500,000 Comparative Preparation Example 5 79.95 - - - - - 0.05 - - 20 - Insolubilized (separated into two phases) - - AM: Acrylamide ("50% Acrylamide" made by Mitsubishi Chemical Corporation)
- DMAA: N,N-dimethylacrylamide ("DMAA" made by KJ Chemicals Corporation)
- MEA: 2-methoxyethyl acrylate ("2-MTA" made by Osaka Organic Chemical Industry Ltd.)
- MMEA: 2-methoxyethyl methacrylate ("2-Methoxyethyl Methacrylate" made by Tokyo Chemical Industry Co., Ltd.)
- MEEA: 2-ethoxyethyl methacrylate ("2-Ethoxyethyl Methacrylate" made by Tokyo Chemical Industry Co., Ltd.)
- AA: Acrylic acid ("80% Acrylic Acid" made by Osaka Organic Chemical Industry Ltd.)
- HEA: 2-hydroxyethyl acrylate ("HEA" made by Osaka Organic Chemical Industry Ltd.)
- AN: Acrylonitrile ("Acrylonitrile" made by Mitsubishi Chemical Corporation)
- BA: Butyl acrylate ("Butyl Acrylate" made by Toagosei Company, Limited)
- SMAS: Sodium methallyl sulfonate
- NaOH: Sodium hydroxide ("48% Sodium Hydroxide Solution" made by Kanto Chemical Co., Inc.)
- A slurry was prepared using a commercially available homodisper ("Homodisper Model 2.5" made by PRIMIX Corporation). In a mayonnaise bottle as a container, the binder aqueous solution for a lithium-ion battery as obtained in Preparation Example 1, which contained the water-soluble poly(meth)acrylamide (A), was mixed in an amount of 5 parts by mass in terms of solid content with 20 parts by mass of silicon monoxide particles ("CC Powder" made by OSAKA Titanium technologies Co., Ltd.) having a D50 (median diameter) of 5 µm, 80 parts by mass of artificial graphite ("G1-A#" made by Jiangxi Zichen Technology Co., Ltd.) having a D50 (median diameter) of 20 µm, and 1 part by mass of a conductive aid ("Super C65" made by Imerys Graphite & Carbon Japan K.K.). Ion-exchanged water was added thereto so as to achieve a solid content concentration of 47%, and the container was set in the above homodisper. Next, the resultant was kneaded at 3,000 rpm for 10 minutes. After that, the resultant was subjected to defoaming for 1 minute using a rotation/revolution mixer ("Awatori Rentaro" made by THINKY CORPORATION), and a slurry for an electrode was obtained.
- In the examples other than Example 1 and the comparative examples, a slurry was prepared in the same manner as in Example 1 except that the composition in Example 1 was changed to those shown in the following table.
- The storage stability of the electrode slurry was evaluated as follows.
- The viscosity (unit: mPa·s) of the electrode slurry was measured by a B-type viscometer and then stored in an oven heated to 40 °C for 3 days. After storage, the viscosity was measured again by the B-type viscometer. A change in viscosity was calculated by the following equation and was evaluated according to the following evaluation criteria.
- A: Less than 110%
- B: 110% or more and less than 120%
- C: 120% or more and less than 130%
- D: 130% or more
- The electrode flexibility was evaluated as follows.
- The above slurry for a lithium-ion battery was uniformly applied to a surface of a current collector (20 µm) composed of copper foil by a doctor blade method so that a film thickness after drying would be 170 µm, then subjected to heating and drying at 150 °C for 15 minutes, and an electrode was obtained. The obtained electrode was cut into a width of 10 mm and a length of 70 mm, and was wound around a Teflon™ rod having a diameter of 30 mm0 with an active material layer facing outward. A state of a surface of the active material layer was observed and evaluated according to the following criteria.
- A: No cracks and peeling occurred at all in the active material layer bound on the current collector.
- B: Cracks were seen in the active material layer bound on the current collector, but no peeling was observed.
- C: Cracks were seen and peeling was observed in the active material layer bound on the current collector.
- The electrode adhesion was evaluated as follows.
- The above slurry for a lithium-ion battery was uniformly applied to a surface of a current collector (20 µm) composed of copper foil by a doctor blade method so that a film thickness after drying would be 170 µm. After drying at 150 °C for 30 minutes, the resultant was subjected to a heating treatment at 150 °C in vacuum for 120 minutes. After that, by press processing with a roll press machine to achieve a film (electrode active material layer) density of 1.5 g/cm3, an electrode was obtained. A test piece of 2 cm in width×10 cm in length was cut out from the obtained electrode and fixed with a coating surface facing up. Next, an adhesive tape ("CELLOTAPE™" made by NICHIBAN Co., Ltd.) (specified in JIS Z1522) of 15 mm in width was attached while being pressed onto a surface of an active material layer of the test piece, and then the stress when the adhesive tape was peeled off from one end of the test piece at a speed of 30 mm/min in the 180 ° direction was measured using a tensile tester ("TENSILON RTM-100" made by A&D Company, Limited) at 25 °C. The measurement was performed twice, the measured stress was converted into a value per width of 15 mm, and an average value thereof was calculated as peel strength. The higher the peel strength, the higher the adhesion strength between the current collector and the active material layer or the binding property between the active materials, indicating that the active material layer is less likely to be peeled from the current collector or the active materials are less likely to be peeled from each other.
- Ratings of the electrode adhesion are described in the table according to the following criteria.
- AA: 41 N/m or more
- A: 30 N/m to 40 N/m
- B: 20 N/m to 30 N/m
- C: Less than 20 N/m
- The above slurry for a lithium-ion battery was uniformly applied to a surface of a current collector (20 µm) composed of copper foil by a doctor blade method so that a film thickness after drying would be 170 µm. After drying at 150 °C for 30 minutes, the resultant was subjected to a heating treatment at 150 °C in vacuum for 120 minutes. After that, by press processing with a roll press machine to achieve a film (electrode active material layer) density of 1.5 g/cm3, an electrode was obtained.
- In an argon-purged glove box, the above electrode was punched and formed to have a diameter of 16 mm, and the resultant was placed inside a packing above an aluminum lower lid of a test cell (made by Nippon Tomcell Co., Ltd.). Next, a separator ("Selion P2010" made by CS Tech Co., Ltd.) composed of a polypropylene porous film punched out to a diameter of 24 mm was placed. Further, after 500 µL of electrolytic solution was poured in so that no air could enter, a commercially available metallic lithium foil punched and formed into a size of 16 mm was placed, and an exterior body of the test cell was fastened and sealed with screws. Thereby, a lithium half-cell was assembled. The electrolytic solution used here was a solution in which LiPF6 was dissolved at a concentration of 1 mol/L in a solvent having a mass ratio of ethylene carbonate to ethyl methyl carbonate of 1/1.
- The lithium half-cell was put in a constant temperature bath set to 25 °C and underwent charging and discharging as follows. The charging was started at a constant current (0.1 C) and was completed (cutoff) when the voltage reached 0.01 V. Next, the discharging was started at a constant current (0.1 C) and was completed (cutoff) when the voltage reached 1.0 V. The above charging and discharging were repeated 30 times.
- In the above measurement conditions, "1 C" indicates a current value at which a cell having a certain electric capacity is discharged at a constant current and the discharging is completed in 1 hour. For example, "0.1 C" means a current value at which it takes 10 hours to complete discharging, and "10 C" means a current value at which it takes 0.1 hour to complete discharging.
-
- Ratings of the discharge capacity retention rate are described in the table according to the following criteria.
- AA: 90% or more
- A: 80% to 89%
- B: 70% to 79%
- C: Less than 70%
Negative electrode active material | Binder aqueous solution | Storage stability of electrode slurry | Electrode flexibility | Electrode adhesion | Discharge capacity retention rate | |||
Artificial graphite | Silicon monoxide | Name | Part by mass | |||||
Part by mass | Part by mass | |||||||
Example 1 | 80 | 20 | Preparation Example 1 | 5 | B | A | A | B |
Example 2 | 80 | 20 | Preparation Example 2 | 5 | A | A | A | A |
Example 3 | 80 | 20 | Preparation Example 3 | 5 | B | A | B | B |
Example 4 | 80 | 20 | Preparation Example 4 | 5 | C | B | B | B |
Example 5 | 80 | 20 | Preparation Example 5 | 5 | A | A | AA | A |
Example 6 | 100 | 0 | Preparation Example 6 | 3 | A | B | A | AA |
Example 7 | 80 | 20 | Preparation Example 7 | 5 | B | B | A | A |
Comparative Example 1 | 80 | 20 | Comparative Preparation Example 1 | 5 | D | C | C | C |
Comparative Example 2 | 80 | 20 | Comparative Preparation Example 2 | 5 | D | C | C | C |
Comparative Example 3 | 80 | 20 | Comparative Preparation Example 3 | 5 | C | B | C | C |
Comparative Example 4 | 80 | 20 | Comparative Preparation Example 4 | 5 | C | C | C | C |
Comparative Example 5 | 80 | 20 | Comparative Preparation Example 5 | 5 | D | C | C | C |
Claims (4)
- A binder aqueous solution for a lithium-ion battery, containing:
a water-soluble poly(meth)acrylamide (A) being a polymer of a monomer group containing, with respect to 100 mol% of the monomer group,30 mol% to 95 mol% of a (meth)acrylamide group-containing compound (a), and5 mol% to 40 mol% of an alkoxyalkyl (meth)acrylate (b) represented by general formula (1),
CH2=C(R1)-CO-O-R2-O-R3 (1)
wherein R1 is a hydrogen atom or a methyl group, R2 is an alkylene group having 1 to 4 carbon atoms, R3 is an alkyl group having 1 to 4 carbon atoms, and a total number of carbon atoms of the groups R1, R2 and R3 is 5 or less. - A slurry for a lithium-ion battery negative electrode, containing the binder aqueous solution for a lithium-ion battery according to claim 1 and a negative electrode active material.
- A negative electrode for a lithium-ion battery, obtained by applying the slurry for a lithium-ion battery negative electrode according to claim 2 to a current collector, and drying and curing the slurry.
- A lithium-ion battery, comprising the negative electrode for a lithium-ion battery according to claim 3.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2019168599 | 2019-09-17 |
Publications (1)
Publication Number | Publication Date |
---|---|
EP3796434A1 true EP3796434A1 (en) | 2021-03-24 |
Family
ID=72517150
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP20196109.1A Pending EP3796434A1 (en) | 2019-09-17 | 2020-09-15 | Binder aqueous solution for lithium-ion battery, slurry for lithium-ion battery negative electrode, negative electrode for lithium-ion battery, and lithium-ion battery |
Country Status (5)
Country | Link |
---|---|
US (1) | US11769866B2 (en) |
EP (1) | EP3796434A1 (en) |
JP (1) | JP2021051997A (en) |
KR (1) | KR102314783B1 (en) |
CN (1) | CN112531163A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP4354555A1 (en) * | 2022-10-11 | 2024-04-17 | SK Innovation Co., Ltd. | Binder for secondary battery, negative electrode for secondary battery including the same, and lithium secondary battery including the same |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113980174A (en) * | 2021-10-29 | 2022-01-28 | 西安交通大学 | Coordinate bond enhanced cathode adhesive and preparation method and application thereof |
WO2024024950A1 (en) * | 2022-07-29 | 2024-02-01 | 富士フイルム株式会社 | Secondary battery binder composition, electrode composition, electrode sheet, and secondary battery, and production methods for said electrode sheet and secondary battery |
WO2024034589A1 (en) * | 2022-08-12 | 2024-02-15 | 荒川化学工業株式会社 | Power storage device binder aqueous solution, power storage device slurry, power storage device electrode, power storage device separator, power storage device separator/electrode laminate, and power storage device |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS593761B2 (en) | 1977-12-28 | 1984-01-26 | 株式会社前川製作所 | signal distribution device |
JP2004185810A (en) | 2001-11-20 | 2004-07-02 | Canon Inc | Electrode material for lithium secondary battery, electrode structural body with the electrode material, secondary battery with the electrode structure, manufacturing method of the electrode material, manufacturing method of the electrode structural body, and manufacturing method of the secondary battery |
JP2005259697A (en) | 2004-03-08 | 2005-09-22 | Samsung Sdi Co Ltd | Anode active material and cathode active material for lithium secondary battery, and lithium secondary battery |
JP2013089437A (en) | 2011-10-18 | 2013-05-13 | Toray Ind Inc | Binder for lithium ion battery electrode, paste for lithium ion battery negative electrode using the same and manufacturing method of lithium ion battery negative electrode |
JP5390336B2 (en) | 2009-10-22 | 2014-01-15 | 信越化学工業株式会社 | Negative electrode material for nonaqueous electrolyte secondary battery, method for producing negative electrode material for nonaqueous electrolyte secondary battery, negative electrode for nonaqueous electrolyte secondary battery, and nonaqueous electrolyte secondary battery |
JP2015106488A (en) | 2013-11-29 | 2015-06-08 | Jsr株式会社 | Slurry for electricity storage device negative electrode and electricity storage device negative electrode, slurry for electricity storage device positive electrode and electricity storage device positive electrode, and electricity storage device |
JP2015118908A (en) | 2013-11-14 | 2015-06-25 | Jsr株式会社 | Binder composition for electricity storage device, slurry for electricity storage device, electricity storage device electrode, separator, and electricity storage device |
WO2015098507A1 (en) | 2013-12-25 | 2015-07-02 | 日本ゼオン株式会社 | Binder composition for lithium ion secondary battery, slurry composition for lithium ion secondary battery, method for manufacturing electrode for secondary battery, and lithium ion secondary battery |
US20180102542A1 (en) * | 2015-04-22 | 2018-04-12 | Toagosei Co., Ltd. | Binder for nonaqueous electrolyte secondary battery electrode, and use thereof |
Family Cites Families (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3836410A (en) * | 1972-03-31 | 1974-09-17 | Ppg Industries Inc | Method of treating titanium-containing structures |
JPH09151216A (en) * | 1995-11-29 | 1997-06-10 | Sanyo Chem Ind Ltd | Water-soluble vinyl polymer |
CN103429628B (en) | 2011-01-06 | 2017-05-24 | 三菱丽阳株式会社 | Modifier for polyvinylidene fluoride, binder resin composition for batteries, secondary cell electrode, and battery |
JP5708872B1 (en) * | 2013-09-24 | 2015-04-30 | 東洋インキScホールディングス株式会社 | Nonaqueous secondary battery binder, nonaqueous secondary battery resin composition, nonaqueous secondary battery separator, nonaqueous secondary battery electrode and nonaqueous secondary battery |
KR20150106488A (en) | 2014-03-11 | 2015-09-22 | 삼성디스플레이 주식회사 | Backlight unit and manufacturing method of the same |
KR20150118908A (en) | 2014-04-14 | 2015-10-23 | 옴니시스템 주식회사 | Method of Producing Name Card Assembly |
KR102246767B1 (en) | 2014-08-13 | 2021-04-30 | 삼성에스디아이 주식회사 | Separator for lithium secondary battery, lithium secondary battery employing the same, and preparing method thereof |
KR102555114B1 (en) | 2014-11-18 | 2023-07-12 | 니폰 제온 가부시키가이샤 | Binder composition for lithium-ion secondary battery electrode |
CN104926184B (en) * | 2015-05-28 | 2017-06-20 | 中铁十局集团第三建设有限公司 | A kind of poly carboxylic acid series water reducer and preparation method thereof |
WO2017047379A1 (en) | 2015-09-16 | 2017-03-23 | 日本ゼオン株式会社 | Binder for all-solid-state secondary batteries, and all-solid-state secondary battery |
EP3370288B1 (en) | 2015-10-30 | 2020-09-09 | Toagosei Co., Ltd. | Binder for nonaqueous electrolyte secondary cell electrode, method for producing binder, and use thereof |
JP6911553B2 (en) * | 2016-06-23 | 2021-07-28 | 荒川化学工業株式会社 | Lithium-ion battery negative electrode slurry and its manufacturing method, lithium-ion battery negative electrode, and lithium-ion battery |
CN107151285B (en) * | 2017-05-19 | 2019-06-04 | 天津亿利科能源科技发展股份有限公司 | Water-soluble drag reducer and the preparation method and application thereof for high-content wax light crude oil |
CN114267836A (en) | 2017-12-18 | 2022-04-01 | 荒川化学工业株式会社 | Thermally crosslinkable binder aqueous solution for lithium ion battery, electrode slurry and method for producing same, electrode for lithium ion battery, and battery |
JP7031278B2 (en) * | 2017-12-18 | 2022-03-08 | 荒川化学工業株式会社 | Binder aqueous solution for lithium ion battery, electrode slurry for lithium ion battery and its manufacturing method, electrode for lithium ion battery, and lithium ion battery |
KR20200135329A (en) * | 2018-03-27 | 2020-12-02 | 니폰 제온 가부시키가이샤 | Method for producing a binder composition for secondary batteries, a slurry composition for a secondary battery functional layer, a secondary battery member, a secondary battery, and a slurry composition for a secondary battery negative electrode |
-
2020
- 2020-09-15 CN CN202010966619.3A patent/CN112531163A/en active Pending
- 2020-09-15 KR KR1020200118295A patent/KR102314783B1/en active IP Right Grant
- 2020-09-15 US US17/020,823 patent/US11769866B2/en active Active
- 2020-09-15 EP EP20196109.1A patent/EP3796434A1/en active Pending
- 2020-09-16 JP JP2020155058A patent/JP2021051997A/en active Pending
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS593761B2 (en) | 1977-12-28 | 1984-01-26 | 株式会社前川製作所 | signal distribution device |
JP2004185810A (en) | 2001-11-20 | 2004-07-02 | Canon Inc | Electrode material for lithium secondary battery, electrode structural body with the electrode material, secondary battery with the electrode structure, manufacturing method of the electrode material, manufacturing method of the electrode structural body, and manufacturing method of the secondary battery |
JP2005259697A (en) | 2004-03-08 | 2005-09-22 | Samsung Sdi Co Ltd | Anode active material and cathode active material for lithium secondary battery, and lithium secondary battery |
JP5390336B2 (en) | 2009-10-22 | 2014-01-15 | 信越化学工業株式会社 | Negative electrode material for nonaqueous electrolyte secondary battery, method for producing negative electrode material for nonaqueous electrolyte secondary battery, negative electrode for nonaqueous electrolyte secondary battery, and nonaqueous electrolyte secondary battery |
JP2013089437A (en) | 2011-10-18 | 2013-05-13 | Toray Ind Inc | Binder for lithium ion battery electrode, paste for lithium ion battery negative electrode using the same and manufacturing method of lithium ion battery negative electrode |
JP2015118908A (en) | 2013-11-14 | 2015-06-25 | Jsr株式会社 | Binder composition for electricity storage device, slurry for electricity storage device, electricity storage device electrode, separator, and electricity storage device |
JP2015106488A (en) | 2013-11-29 | 2015-06-08 | Jsr株式会社 | Slurry for electricity storage device negative electrode and electricity storage device negative electrode, slurry for electricity storage device positive electrode and electricity storage device positive electrode, and electricity storage device |
WO2015098507A1 (en) | 2013-12-25 | 2015-07-02 | 日本ゼオン株式会社 | Binder composition for lithium ion secondary battery, slurry composition for lithium ion secondary battery, method for manufacturing electrode for secondary battery, and lithium ion secondary battery |
US20180102542A1 (en) * | 2015-04-22 | 2018-04-12 | Toagosei Co., Ltd. | Binder for nonaqueous electrolyte secondary battery electrode, and use thereof |
Non-Patent Citations (2)
Title |
---|
"Handbook of Chemistry: Pure Chemistry II", CHEMICAL SOCIETY OF JAPAN, pages: 325 |
ZHIXIONG YANG ET AL: "Polyelectrolyte Binder for Sulfur Cathode To Improve the Cycle Performance and Discharge Property of Lithium-Sulfur Battery", ACS APPLIED MATERIALS & INTERFACES, vol. 10, no. 16, 4 April 2018 (2018-04-04), US, pages 13519 - 13527, XP055759695, ISSN: 1944-8244, DOI: 10.1021/acsami.8b01163 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP4354555A1 (en) * | 2022-10-11 | 2024-04-17 | SK Innovation Co., Ltd. | Binder for secondary battery, negative electrode for secondary battery including the same, and lithium secondary battery including the same |
Also Published As
Publication number | Publication date |
---|---|
US11769866B2 (en) | 2023-09-26 |
JP2021051997A (en) | 2021-04-01 |
CN112531163A (en) | 2021-03-19 |
KR20210032912A (en) | 2021-03-25 |
US20210083262A1 (en) | 2021-03-18 |
KR102314783B1 (en) | 2021-10-19 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6888656B2 (en) | Binder aqueous solution for lithium ion battery, slurry for lithium ion battery electrode and its manufacturing method, lithium ion battery electrode, and lithium ion battery | |
US11637288B2 (en) | Thermally crosslinkable binder aqueous solution for lithium-ion battery, thermally crosslinkable slurry for lithium-ion battery negative electrode, negative electrode for lithium-ion battery, lithium-ion battery negative electrode material, and lithium-ion battery and method for producing the same | |
US11658302B2 (en) | Conductive carbon material dispersing agent for lithium ion battery, slurry for lithium ion battery electrode, electrode for lithium ion battery, and lithium ion battery | |
US11769866B2 (en) | Binder aqueous solution including copolymer of (meth)acrylamide and alkoxyalkyl (meth)acrylate, slurry including the same, negative electrode, and lithium-ion battery | |
US11962010B2 (en) | Binder aqueous solution for lithium-ion battery electrode, slurry for lithium-ion battery electrode, lithium-ion battery electrode, and lithium-ion battery | |
US11646421B2 (en) | Thermally crosslinkable binder aqueous solution for lithium-ion battery, thermally crosslinkable slurry for lithium-ion battery negative electrode, negative electrode for lithium-ion battery | |
JP7215348B2 (en) | Thermally crosslinkable binder aqueous solution for lithium ion battery, electrode thermally crosslinkable slurry for lithium ion battery, electrode for lithium ion battery, and lithium ion battery | |
US11670776B2 (en) | Binder aqueous solution for lithium-ion battery electrode, slurry for lithium-ion battery negative electrode, negative electrode for lithium-ion battery, and lithium-ion battery | |
EP3890076A1 (en) | Binder aqueous solution for lithium ion battery, slurry for negative electrode of lithium ion battery, negative electrode for lithium ion battery, and lithium ion battery | |
US12107271B2 (en) | Binder aqueous solution for lithium ion battery, slurry for negative electrode of lithium ion battery, negative electrode for lithium ion battery, and lithium ion battery |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION HAS BEEN PUBLISHED |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
AX | Request for extension of the european patent |
Extension state: BA ME |
|
17P | Request for examination filed |
Effective date: 20210310 |
|
RBV | Designated contracting states (corrected) |
Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: EXAMINATION IS IN PROGRESS |
|
17Q | First examination report despatched |
Effective date: 20231026 |